High pressure synthesis of phosphine from the elements and the discovery of the missing (PH3)2H2 tile

High pressure reactivity of phosphorus and hydrogen is relevant to fundamental chemistry, energy conversion and storage, and materials science. Here we report the synthesis of (PH3)2H2, a crystalline van der Waals (vdW) compound (I4cm) made of PH3 and H2 molecules, in a Diamond Anvil Cell by direct catalyst-free high pressure (1.2 GPa) and high temperature (T ≲ 1000 K) chemical reaction of black phosphorus and liquid hydrogen, followed by room T compression above 3.5 GPa. Group 15 elements were previously not known to form H2-containing vdW compounds of their molecular hydrides. The observation of (PH3)2H2, identified by synchrotron X-ray diffraction and vibrational spectroscopy (FTIR, Raman), therefore represents the discovery of a previously missing tile, specifically corresponding to P for pnictogens, in the ability of non-metallic elements to form such compounds. Significant chemical implications encompass reactivity of the elements under extreme conditions, with the observation of the P analogue of the Haber-Bosch reaction for N, fundamental bond theory, and predicted high pressure superconductivity in P-H systems.

superconductivity in phosphine (T c > 100 K, P > 200 GPa) 36 , has stimulated several theoretical studies aimed at exploring the structure and stability of PH 3 at high pressure and the substantially unknown high pressure behavior of the phosphorus-hydrogen system, with the prediction of superconducting layered structures formed by these two elements above 80 GPa [37][38][39] .
Finally, the formation, stability and decomposition of PH 3 in presence of H 2 are relevant astrochemical issues 40 related to the composition of giant planets, such as Jupiter and Saturn 41,42 , and their moons 43 , where PH 3 and H 2 have been detected.
Within this picture, in this paper we report a synchrotron XRD and vibrational spectroscopy (FTIR and Raman) study of the high pressure chemistry occurring between black phosphorus and molecular hydrogen at pressure of 1.2-1.5 GPa and temperature ≲1000 K, where phosphorus is in the layered crystalline orthorhombic structure (A17), commonly known as black phosphorus, and H 2 is liquid 44 (Fig. 1). In these thermodynamic conditions PH 3 is directly synthesized from the elements. On further room T compression, between 3.5 and 4.1 GPa, PH 3    excess H 2 to form the crystalline vdW compound (PH 3 ) 2 H 2 , whose identification has remarkable implications. Pressure was statically generated by means of membrane DAC and temperature by laser heating (LH), with P black acting at the same time as reactant and laser absorber and H 2 as a reactant and pressure transmitting medium.

Results
X-Ray Diffraction. After loading (see "Methods"), the sample of P black and H 2 was compressed to 1.2 GPa, where three laser irradiations were performed. The irradiations power (<3 W at laser output) and duration (up to~30 s) were carefully increased up to visually observe the real time chemical transformation of the sample, which occurred in the 900 ± 100 K temperature interval, with only a slight pressure drift from 1.2 to 1.3 GPa, and then to 1.5 GPa, respectively, after the second (LH2) and third (LH3) irradiation ( Fig. 1). Each irradiation produced an increasing transformation of P black , as confirmed by the intensity decrease of the P black peaks in the diffraction patterns acquired before and after laser heating. After LH3 the absence of diffraction peaks indicated the complete consumption of P black , suggesting the formation of an amorphous or liquid product in the laser heated area (Fig. 2).
The sample was then compressed at room T and between 3.5 and 4.1 GPa the sudden appearance of single diffraction spots in the detector image, observed up to the highest explored pressure (5.5 GPa), unambiguously marked the formation of a crystalline product (Fig. 2). A careful XRD mapping of the sample over a grid with 10 μm spacing was performed to identify the regions where single spot diffraction could be observed. These regions were further explored by higher resolution mapping (4 μm spacing grid) and single-crystal patterns acquired on selected points of the laser heated area.
The first reaction product that we thought about was of course PH 3 . Unfortunately, even if PH 3 is expected to solidify at higher pressure with respect to NH 3 (1.0 GPa) due to the smaller electric dipole moment and to the absence of H-bonding 45,46 , the solidification pressure of PH 3 at room T is unknown.
Furthermore, the high pressure structure of solid PH 3 is also unknown and only ambient pressure low T XRD data by Natta and Casazza dating back to 1930 47 are available in the literature, indicating that PH 3 crystallizes into a compact packing face centered cubic structure, possibly belonging to space group T 2 h (Pn 3, P2/n 3, n. 201) or O 4 h (Pn 3m, P4 2 /n 3 2/m, n. 224), none of which is compatible with our single-crystal data (Supplementary Note 2).
Even considering the P positions in the I4cm and I4/mcm structures obtained from the single-crystal data as occupied by PH 3 molecules, some inconsistencies emerge with a compact packing structure. Indeed, assuming orientationally disordered spherical shaped PH 3 molecules in contact with each other, deriving the molecular volume using as molecular radius half of the shortest distance between P atoms ((4/3)π(3.608/2) 3 = 24.592 Å 3 , in agreement with literature 48,49 ), and considering 8 molecules per unit cell, then a filled volume of 196.736 Å 3 out of the 366.36 Å 3 unit cell volume obtained from the single-crystal data can be estimated, corresponding to a 0.537 filling ratio, which is significantly lower than the 0.74 ratio expected for a close packing structure.
This occurrence, indicating the presence of free volume, which can not be accounted for by a compact packing of PH 3 , provided the first hints suggesting the presence of interactions between PH 3 molecules and a different composition of our reaction product, as indeed confirmed by the spectroscopic data.
Even if the infrared bands of solid PH 3 have been measured only at low T 50,51 and those of liquid PH 3 only at low temperature and modest high pressure (up to 35 atm) 52 , the bands observed at 983,~1100, 2358, and 3466 cm −1 can be confidently assigned to the fundamental and combination vibrational modes of PH 3 , as indicated in Table 1.
Finally, the two remaining bands at 3346 and 4121 cm −1 can not be assigned either to PH 3 or H 2 (Supplementary Note 3).
On decompression from 6.7 to 3.1 GPa, below the crystallization threshold of the reaction product, the two extra bands at 3346 cm −1 and 4121 cm −1 disappear. All the other bands of PH 3 exhibit a high-frequency shift, as typically observed in H-bonded systems when releasing pressure, and the bands of H 2 a lowfrequency shift, as expected. On further decompression to ambient conditions, both PH 3 and H 2 bands shift to lower frequency, until disappearing with the opening of the cell.
No bands could be detected in the FTIR spectra after completely releasing the membrane pressure and opening/closing the cell under glove box in an inert atmosphere.
Raman spectroscopy. A detailed Raman mapping, consisting of a 130 × 130 μm 2 mesh with 10 μm grid spacing, was performed to gain insight about the reaction products and their spatial distribution within the sample at each pressure point during decompression, covering the entire frequency range between 40 and 4700 cm −1 . The analysis of the Raman spectra acquired across the sample at 6.8 GPa revealed the presence of two limit spectra, referred to in the following respectively as type-1 and type-2 Raman spectra, and a variety of combinations of them, with significant bands in three spectral regions: 200-1250 cm −1 , 2000-2600 cm −1 , and 4000-4300 cm −1 ( Fig. 3 and Supplementary Fig. 5).
Type-2 Raman spectrum exhibits additional bands at 984, 1114, and 2352 cm −1 , which can be readily assigned respectively to the ν 2 , ν 4 and ν 1 : ν 3 fundamental modes of PH 3 51 , consistently with the IR spectra (Fig. 3, lower panel, blue trace). However, differently from the IR spectra, no combination bands of PH 3 are detected in the Raman spectra. The Raman band at 4123 cm −1 , observed only in type-2 Raman spectra together with the presence of PH 3 , almost exactly matches the corresponding IR absorption band at 4121 cm −1 (6.7 GPa) and can not be assigned either to P, H 2 or PH 3 .
As in the case of the IR spectra, during decompression to 3.1 GPa, below the crystallization pressure of the reaction product observed by XRD, the extra band at 4123 cm −1 disappears, while the bands of PH 3 exhibit a high-frequency shift ( Supplementary  Fig. 5) and those of H 2 a low-frequency shift. Both PH 3 and H 2 bands frequencies all undergo a low-frequency shift on further decompression and disappear after opening the cell. At 1.95 GPa three sharp bands, unambiguously identified as the characteristic A ð1Þ g , E g and A ð2Þ g signatures of P black , respectively appear at 373, 443, and 467 cm −1 , remaining observable on decompression down to ambient pressure ( Supplementary Fig. 5). Even if the detection of these three peaks could suggest an incomplete transformation of P black and its missed observation, the  The spectra have been vertically translated for clarity and the values on the absorbance scale are intended for relative comparison. The break on the wavenumber axis excludes the spectral range corresponding to the Ia diamond saturating absorptions, which partially covers the ν 4 absorption of PH 3 . The absorption features at~2640 cm −1 (6.7 GPa) and~2900 cm −1 (appearing on releasing pressure to 3.1 GPa) are assigned respectively to the diamond from the ambient pressure reference and to traces of oil on the optics of the interferometer. b Significant spectral regions of type-1 (red, lower trace) and type-2 (blue, upper trace) Raman spectra acquired on different selected spots of the mapping grid across the sample at 6.8 GPa and room T after LH. With respect to type-1 spectrum the type-2 one clearly shows the simultaneous presence of PH 3 and of the extra band at 4123 cm −1 in the H 2 stretching region at lower frequency compared to pure H 2 .
Raman spectra acquired at 0.2 GPa and at ambient pressure on the recovered sample show characteristic bands at~385 cm −1 , which is not present in any of the P red forms nor in P black ( Supplementary  Fig. 7), and at 2245 cm −1 in the P-H stretching region, which closely resemble the Raman spectra reported by Yuan and coauthors for the recovered products of the decomposition of PH 3 quenched from 25 GPa to 31 GPa 55 ( Supplementary Fig. 8), thus suggesting a laser-induced decomposition of PH 3 during the acquisition of the Raman spectra, after releasing pressure below the crystallization threshold of the reaction product. Interestingly, the P-H stretching band observed at 2200 cm −1 at 6.8 GPa exhibits a high-frequency shift to~2226 cm −1 on releasing pressure to 3.1 GPa, which further increases to 2245 cm −1 on releasing pressure to ambient conditions ( Supplementary Fig. 5), providing evidence of the presence of H-bonding in the recovered solid product. Unfortunately, no additional insight could be gained on the recovered solid material responsible for type-1 Raman spectrum, which appears to consists of a hydrogenated (Hfunctionalized) mixture of amorphous P red and crystalline P black .

Discussion
Our data provide clear experimental evidence for direct highpressure and high-temperature chemical reactivity between elemental P black and H 2 . The resulting formation of PH 3 according to the following chemical equation P þ 3 2 H 2 1:2 GPa;1000 K À À À À À À ÀÀ ÀÀ ÀÀ! no catalyst PH 3 ð1Þ represents the so far unreported catalyst-free phosphorus analogue of the nitrogen-based Haber-Bosch reaction for the synthesis of NH 3 (Supplementary Note 9). Compressing PH 3 in excess H 2 at room T, between 3.5 and 4.1 GPa, the XRD data indicate the crystallization of a reaction product. As type-1 Raman spectrum was assigned to an amorphous solid product, we related the X-ray diffraction pattern of our crystalline product to type-2 Raman spectra, in which PH 3 is observed, and considered the P positions of the corresponding structure to be occupied by PH 3 molecules. The presence of PH 3 in type-2 Raman spectra is always associated to the detection of an extra band in the H 2 stretching region at lower frequency compared to pure H 2 , which disappears on releasing pressure below the crystallization threshold of the crystalline reaction product. A similar behavior is observed in the IR spectra, where an extra band is detected at 4121 cm −1 (6.7 GPa), almost exactly coinciding with the frequency of the extra Raman band at 4123 cm −1 (6.8 GPa).
Whereas the sharp higher frequency band perfectly matches with the literature data about H 2 molecules in crystalline phase I (4250 cm −1 in IR and 4212 cm −1 in Raman at 6.8 GPa) 56 , the unassigned and unexpected broader extra band at lower frequency (4121 cm −1 at 6.7 GPa in IR and 4123 cm −1 at 6.8 GPa in Raman), indicates the presence of a second type of H 2 molecules, which experience a significant weakening of the bond force constant (5.15%, average value between 4.30% Raman and 6.00% IR weakening), likely due to a different local force field, as indeed consistently attested by their larger bandwidth in comparison to pure H 2 .
A possible interpretation for this occurrence is the formation of a van der Waals crystalline compound made of PH 3 and H 2 molecules with (PH 3 ) 2 H 2 stoichiometry and a tetragonal Al 2 Culike structure belonging to I4cm space group 26 , where PH 3 and H 2 respectively occupy 8c (C s ) and 4a (C 4 ) Wyckoff sites (Fig. 4). In this structure four molecules of PH 3 are located on a plane parallel to the [a, b] direction at 0.5z and occupy the positions around a 4-fold rotation axis (C 4 ) along the c direction. Four additional molecules occupy the positions generated by a rotation along C 4 and a translation along +0.5z, giving rise to alternatively rotated layers of PH 3 molecules.
This interpretation of our data is in agreement with the I4cm tetragonal structure of P atoms obtained from the single-crystal data and also accounts for the existence of free volume in the unit cell, in the case PH 3 only would be present.
Furthermore, in this structure the H 2 molecules are encaged within square antiprismatic voids delimited by eight PH 3 molecules (four on one layer and four on the adjacent layer) and occupy a single type of crystal site (C 4 ), corresponding to 4a Wyckoff positions, whose occupancy, according to group theory, is consistent with the appearance of one infrared and Raman active crystal component for the H 2 stretching vibration (Supplementary Note 6 and Supplementary Fig. 10).
In addition, the occupation by PH 3 molecules of 8c Wyckoff sites (C s ), is consistent with the splitting of the (ν 1 + ν 4 );(ν 3 + ν 4 ) combination band. The extra band observed in the IR spectra at 3346 cm −1 at 6.8 GPa, disappearing on decompression to 3.1 GPa, can be thus assigned to PH 3 molecules forming the (PH 3 ) 2 H 2 crystal structure (Supplementary Note 6 and Supplementary Fig. 10).
A density of 1.269 g cm −3 can be calculated at 5.5 GPa from the refinement of the single-crystal data, with 2.89% in weight of H 2 and total 11.5% in weight of H (H 2 + H in PH 3 ).
The molecular nature of the reaction product is further confirmed by the bulk modulus B = 6.7 ± 0.8 GPa derived from the 2nd order Birch-Murnaghan equation of state in the investigated pressure range, which is in absolute agreement with analogous systems 26 , and by the pressure evolution of the nearly constant c/a axial ratio, which indicates an almost isotropic compression within the applied pressure range (Supplementary Note 7). Pressure has greatly extended the number of known hydrides synthesized under high-density conditions 15,33 . Among non metallic elements, H 2 -containing hydrides have been reported so far in literature for elements ranging from group 14 to group 18 of the periodic table, and include van der Waals hydrides of noble gases, simple diatomic molecules, and covalent molecular hydrides ( Supplementary Fig. 16).
If among these hydrides we only consider those involving elements which are able to form covalent molecular hydrides ( Supplementary Fig. 17) and particularly focus on those which have been reported to adopt a I4cm (I4/mcm) crystal structure with X 2 H 2 composition, where X represents the corresponding molecular hydride (Supplementary Fig. 18), then we observe that this structure has been experimentally reported in the case of: carbon, with methane (CH 4 ) 19 , for group 14; sulphur, with H 2 S 26 , and selenium, with H 2 Se 27 , for group 16; and iodine, with HI 57 , for group 17. Interestingly, to the best of our knowledge no such structure has been reported so far for any of the elements of group 15.
In particular (CH 4 ) 2 H 2 , (H 2 S) 2 H 2 , (H 2 Se) 2 H 2 and (HI) 2 H 2 all reportedly exhibit the same I4/mcm structure, with the H 2 and X molecules respectively occupying 4a and 8h Wyckoff positions, whereas (PH 3 ) 2 H 2 exhibits a I4cm structure with the H 2 and PH 3 molecules occupying the 4a and 8c Wyckoff positions. The I4cm and I4/mcm structures are closely related and only differ for the presence of an inversion center in I4/mcm, with identical lattice parameters and atomic positions. Noticeably, even if the occupation of 8h Wyckoff positions of C 2v site symmetry by CH 4 , H 2 S, H 2 Se and HI, respectively in (CH 4 ) 2 H 2 , (H 2 S) 2 H 2 , (H 2 Se) 2 H 2 and (HI) 2 H 2 does not rise any symmetry issue (such as in the case of PH 3 (C 3v ) occupying a C 2v site in the I4/mcm structure), no infrared spectra for any of these compounds have been acquired in the H 2 stretching region, where, according to the analysis of the Davydov components activity using group theory arguments, the appearance of an extra band would unambiguously support the formation of a structure belonging to the I4cm rather than to the I4/mcm space group (Supplementary Note 6). Indeed, the possibility of the I4cm lower symmetry structure has been proposed also for (H 2 S) 2 H 2 26 , whereas the I4/mcm structures of (H 2 Se) 2 H 2 and (HI) 2 H 2 were assigned according to similarity with (H 2 S) 2 H 2 , thus suggesting all these structures to belong to I4cm rather than I4/mcm space group. Furthermore, the consistency of the IR and Raman optical activity with the application of group theory to the crystal symmetry, indicates that the PH 3 molecules are not randomly oriented and that their orientations reflect the symmetry and periodicity of the intermolecular potential originating from their symmetry. This apparently contrasts with the orientational disorder reported for CH 4 , H 2 S, H 2 Se, and HI, respectively, in (CH 4 ) 2 H 2 , (H 2 S) 2 H 2 , (H 2 Se) 2 H 2, and (HI) 2 H 2 , which has been speculated from the behavior of the pure hydrides, without any conclusive evidence to support it like IR absorption spectra in the H 2 stretching region (Supplementary Note 10) 58,59 .
The identification of (PH 3 ) 2 H 2 thus represents the discovery of the missing tile for group 15, specifically corresponding to phosphorus, in the puzzle of the periodic properties of nonmetallic elements, which are able to form van der Waals molecular compounds containing their covalent hydrides and H 2 molecules (Fig. 5). A further chemical insight can be gained from the Raman data. All these five X 2 H 2 isostructural compounds feature the extra Raman band in the H 2 stretching region, due to the vibration of the H 2 molecules inside their structure, in addition to the signal of the surrounding pure H 2 , which is always present as excess reactant from the synthesis. These frequencies are listed in the Table in Fig. 6, together with the corresponding frequency shift with respect to pure H 2 . An interesting feature emerging from this comparison is that, at similar high-pressure conditions, the frequency shift of the extra band with respect to pure H 2 is always negative, except in the case of methane. According to the valence shell electron pair repulsion (VSEPR) theory, and to the fulfillment of the octet rule for the outer electronic shell 45 , the main difference between methane and the other hydrides is that methane does not possess an electron lone pair on carbon, whereas PH 3 , H 2 S, H 2 Se and HI all have at least one electron lone pair on the hydride forming element (Fig. 6).
The presence of lone pairs is typically associated to the ability of forming H-bonding, as indeed observed for all these systems, and of behaving as an electron donor Lewis base. H-bonding between the corresponding hydride molecules, evidenced by a negative frequency shift with increasing pressure of the internal stretching modes involving H atoms, has been indeed reported for (H 2 S) 2 H 2 , (H 2 Se) 2 H 2 , and (HI) 2 H 2 .
The high-frequency shift, observed both in the infrared and Raman spectra acquired on releasing pressure from 6.8 to 3.1 GPa across the melting threshold of the crystalline product (Supplementary Fig. 6), suggests also PH 3 to behave like the analogous X 2 H 2 isostructural van der Waals compounds, exhibiting H 3 P ⋯ H-PH 2 H-bonding interactions, which disappear on decompression from 6.8 to 3.1 GPa after the decomposition of (PH 3 ) 2 H 2 , as attested by the decrease of the vibrational frequencies of PH 3 on further decompression.
The presence of a H-bonding between PH 3 molecules has noticeable chemical relevance as PH 3 , in contrast to NH 3 , is known for not forming H-bonding at ambient conditions 45,46 , due to the small electronegativity difference of phosphorus with respect to hydrogen and to the consequent smaller electric dipole moment 60 . Furthermore, the existence of such interaction, together with the presence of H 2 molecules, is in agreement with the larger volume of the crystalline cell of (PH 3 ) 2 H 2 compared to what expected in pure PH 3 .
The softening of the stretching vibration in the H 2 molecules forming the (PH 3 ) 2 H 2 crystal clearly indicates the presence of chemical interaction between H 2 and PH 3 . In the case of the isolated molecules such interaction has been described by ab initio computational methods 61 in terms of two possible contributions: 1) the electron lone pair of P can act as a Lewis base and the σ * anti-bonding molecular orbital of H 2 as a Lewis acid (n → σ * ); 2) the σ bonding molecular orbital electrons of H 2 act as Lewis base and the first anti-bonding molecular orbital of PH 3 as a Lewis acid (σ → σ * (H-PH 2 )).
The first interaction is essentially a HOMO-LUMO orbital overlap interaction involving the highest occupied molecular orbital (HOMO) of PH 3 (2a 1 symmetry), which hosts the electron lone pair and has a prevalent non-bonding character, and the unoccupied σ * anti-bonding molecular orbital of H 2 , technically the lowest unoccupied molecular orbital (LUMO), whereas the second one corresponds to the opposite situation, where the HOMO σ bond electron density of H 2 interacts with the LUMO orbital of PH 3 (3a 1 ) (Fig. 7). Energetically, the first interaction is larger when the 2a 1 HOMO of PH 3 and the σ * of H 2 have maximum overlap, with the electron lone pair and the molecular axis of H 2 aligned, but is present, even to a smaller extent, also in other interaction configurations, whereas the second one requires the σ electron density of H 2 to interact with the 3a 1 LUMO of PH 3 in a configuration where the electron lone pair is perpendicular to H 2 molecular axis.
In solid state, as group 15 elements are concerned, the first kind of interaction has been recently reported to be responsible for the softening of the H 2 stretching vibration in the As 4 O 6 ⋅ 2H 2 crystal by electron density transfer from the As electron lone pair to the σ * anti-bonding orbital of H 2 62 . Gúnka et al. achieved this result by adopting the ICOHP (integrated projected crystal orbital Hamilton population) and ICOOP (integrated projected crystal orbital overlap population) computational methods, which, based on the crystal orbital overlap population (COOP) approach originally developed by R. Hoffmann 63 , indeed relate the local molecular orbitals to the band structure of crystals through the projection decomposition of the electron density of states,  allowing to gain insight about the frontier orbitals that control structure and reactivity in extended systems. Accordingly, a qualitative interpretation for the softening of the stretching vibration of the H 2 molecules in the (PH 3 ) 2 H 2 crystal, certainly deserving appropriate theoretical investigation for effective electronic band structure calculation, is here proposed in terms of isolobal frontier molecular orbital overlap interaction between the HOMO of PH 3 , hosting the electron lone pair, and the σ * anti-bonding LUMO of H 2 (Fig. 7). Even if the orientation of PH 3 and H 2 molecules is not known, considering that H 2 is expected to undergo hindered rotations at this pressure, it is indeed likely that the 2a 1 HOMO of some of the PH 3 molecules building up the cavities, where the H 2 molecules are hosted, and the σ * anti-bonding orbital of H 2 dynamically adopt the correct orientation for an effective overlap. The σ * anti-bonding orbital of H 2 is normally not occupied, which makes the H 2 molecule stable. The electron density transfer from the lone pair of PH 3 to the σ * anti-bonding orbital of H 2 may decrease the bonding electron density of the H 2 molecule, thus causing a reduction of the force constant (~5.15%) and finally a frequency decrease of the H 2 stretching mode, according to the harmonic oscillator frequency ). The existence of the σ(H 2 ) → σ * (H-PH 2 ) interaction may further contribute to this effect. As a result, the H 2 molecules within the crystal structures of (PH 3 ) 2 H 2 exhibit a lower vibrational frequency compared to bulk solid H 2 .
Finally, the observation of (PH 3 ) 2 H 2 is also somehow relevant for superconductivity in PH 3 . PH 3 has been experimentally reported to become metallic at 40 GPa and superconducting at 207 GPa with a T c of 103 K, but with no structural characterization so far 36 . Since then quite a lot of theoretical efforts have been made to account for such observation. At the moment, theory and experiments seem to agree about the instability of pure PH 3 at high pressure, whose decomposition proceeds through the release of H 2 . Experimentally, a couple of recent papers have reported the decomposition of PH 3 55,64 , with the initial formation of diphosphane followed by decomposition into elemental phosphorus and H 2 . However, no further convincing characterization was proposed, suggesting that, like in the case of H 2 S, other species may be responsible for the superconductivity observed by Drozdov et al. 36 . Theoretically, besides predicting the decomposition of PH 3 , different studies have calculated the stabilization of PH 2 phases above 80 GPa, which, from a stoichiometric point of view, is consistent with the release of H 2 37,38 . Furthermore, a key role of molecular H 2 in stabilizing the highpressure superconducting phases of phosphorus hydrides has been recently proposed 39 . Interestingly, even if the pressure range is here much lower, our data show that PH 3 and H 2 form a crystalline vdW compound, in which molecular H 2 is indeed involved, possibly stabilizing PH 3 , or other related species, even at higher pressure.
To summarize, the results of this study have multiple chemically relevant implications. First of all, using LH in DAC, we have successfully induced direct reactivity between P black and H 2 at 1.2 GPa and temperature lower than 1000 K, without the use of any catalyst or precursor. To our knowledge this is the first report about a direct chemical reaction between P black , the thermodynamically stable allotrope of P, and H 2 at high pressure and high temperature to form PH 3 , somehow mimicking and representing the P analogue of the Haber-Bosch process for the synthesis of NH 3 from N 2 and H 2 . Secondly, at room T and pressure between 3.5 and 4.1 GPa PH 3 combines with excess H 2 to form the crystalline (PH 3 ) 2 H 2 van der Waals compound, whose observation consistently fills a gap existing for pnictogens in the periodic properties of non-metallic elements able to form crystalline vdW compounds made of the corresponding hydride and of molecular hydrogen. The identification of (PH 3 ) 2 H 2 represents the so far missing tile of P in this puzzle and confirms a general trend in the formation of H 2containing vdW compounds with X 2 H 2 stoichiometry (X = molecular hydride) and I4cm (I4/mcm) structure.
The formation of unexpected chemical compounds made of components apparently non-interacting at ambient conditions, such as P and H, is extremely important for their relevant implications, which include H 2 storage, the chemistry occurring in extraterrestrial environments of giant planets such as Jupiter, Saturn, and their moons, where PH 3 and H 2 are present 40,41,43 , and the identification of astrochemical processes leading to the synthesis of phosphine, which is a critical issue for the detection of the presence of life in harsh extraterrestrial environments of rocky planets, as inferred by the recent observation of anomalous high levels of phosphine in the cloud decks of Venus atmosphere 65 .
Third, as advancement in fundamental bond theory is concerned, the relevant observation of H-bonding in PH 3 , which in contrast to NH 3 is not reported to exist at ambient pressure, and the existence of a molecular orbital interaction between the electron lone pair in PH 3 and the antibonding molecular orbital of H 2 , provide remarkable insights to understand the effects underlying the predicted stabilization of the P-H systems under high-pressure conditions.
Finally, the synthesis of (PH 3 ) 2 H 2 effectively provides confirmatory experimental evidence for the key role played by H 2 molecules in stabilizing the PH system at high pressure, as suggested by recent calculations predicting the presence of H 2 units in superconducting PH structures at high pressure.
Once again the history of phosphorus has intertwined with pressure, whose role in enhancing similarities and consistencies in the periodic properties of elements apparently exhibiting particular behavior at ambient conditions 5,66,67 is here further highlighted.

Methods
Synthesis of P black . Pure crystalline P black was synthesized from red phosphorus according to reference 68 . All the reactants used for the synthesis of P black were purchased from Sigma-Aldrich with the following purity: red phosphorus (>99.99%), tin (>99.999%), gold (>99.99%), and SnI 4 (99.999%). The purity of the synthesized P black crystals was checked by X-ray powder diffraction, Raman spectroscopy, EDX analysis and ICP-MS measurements, the latter giving a purity of 99.999+%. The crystals of P black were fragmented by means of a metallic tip for obtaining smaller 20-40 μm chips to be loaded into the DAC.
Sample preparation and the experimental conditions. Pressure was generated by means of membrane Diamond Anvil Cells (DAC) equipped with Ia type standard cut 16-sided beveled anvils having 600 μm culets. Re gaskets 200 μm thick were indented to 80 μm thickness and laser-drilled to obtain a 300 μm sample chamber. Before using them for the sideways containment of the samples, a Au ring was applied to prevent unintended catalytic effect and H 2 diffusion and reactivity with Re. For this purpose the 300 μm diameter gasket hole was filled with Au powder, compressed with~20 bar of He in the membrane until the powder appeared reflective and then laser-drilled again to obtain a 250 μm diameter hole. A small crystal of P black was placed in the sample chamber by means of a metallic tip and the remaining volume was filled with fluid H 2 using standard gas-loading technique. Au and a ruby chip were used to measure the pressure, whereas the temperature was measured by the fit of the black body thermal radiation emission of the sample during laser heating. High temperature was generated by means of Nd: YAG laser source (λ = 1064 nm) focused on the P black crystal (≈30 μm beam spot size diameter), which acted both as reactant and laser absorber, thus avoiding any other source of contamination. No evidence for the formation of Au 69 or Re 70 hydrides was observed.
X-ray diffraction data acquisition and analysis. XRD experiments were carried out at the ESRF-ID27 beamline using a monochromatic synchrotron radiation beam (λ = 0.3738 Å) focused to~5 μm to select different areas of the heterogeneous sample. The diffracted radiation was revealed by a MAR CCD165 detector, located approximately at 187 mm from the sample. The setup was calibrated against a CeO 2 powder standard and Dioptas software was used to integrate the 2D area images to 1D patterns.
A single-crystal data set was collected at 5.5 GPa. Diffraction intensities were acquired in an ω-oscillation scan mode over the range ±30 ∘ with a frame width of 0.5 ∘ and an exposure time of 2 s per single frame. The instrument model was calibrated at the beginning of the beam time by performing a full data collection of an enstatite single-crystal placed in a dummy DAC. The diffraction images were then imported into a CrysAlisPro suite (Supplementary Note 1) and processed accordingly. After determining the unit cell the intensities were reduced applying corrections for Lorentz and polarization effects, and also a multiscan absorption correction at the final step. Reciprocal lattice layers were reconstructed using the unwarp procedure ( Supplementary Fig. 1). Careful inspection of the unwarped images did not reveal any twinning, satellite reflections or diffuse scattering, in contrast to the crystal of (H 2 Se) 2 H 2 , where diffuse scattering streaks were observed 27 . The crystal structure was subsequently solved by direct methods and then refined on F 2 by full-matrix least-squares procedures using the SHELXL package (Supplementary Note 1). In addition, at the same pressure and at two other pressure points Spectroscopic data acquisition and analysis. The Raman spectra were acquired at LENS with 1.5 cm −1 spectral resolution using the 647.1 nm emission wavelengths of a Kr ion laser. The details of the Raman setup are described elsewhere 71 . Raman spectra were acquired performing a 14 × 14 mapping over a 10 μm spaced grid using a single 300 groove/mm grating, which allowed to cover the 200-3300 cm −1 frequency region with 4 cm −1 spectral resolution. The most significant spots of the mapping were further inspected at higher resolution (1.5 cm −1 ) with different grating configuration down to 23.5 cm −1 (triple grating subtractive configuration 900-900-1800 groove/ mm) and up to 4700 cm −1 (single grating configuration 900 groove/mm). No photochemical effect was observed at the employed laser power (1.5 mW) for pressure higher than 1.9 GPa, whereas at this pressure the formation of P black could indicate the decomposition of PH 3 55 .
The FTIR spectra were acquired with 1 cm −1 spectral resolution, using a Bruker IFS-120HR interferometer, suitably modified for the acquisition of infrared absorption spectra at high pressure in DAC 72 .
The frequency and intensity of the FTIR and Raman bands were obtained by fitting procedure using Voigt line shapes after baseline subtraction. Fityk software was used for this purpose.