Abstract:Treatment of dithiophosphoric acid diesters (RO)2P(S)SH with appropriate quantities of tris[(phosphine)gold(I)]oxoniumtetrafluoroborates {[(R'3P)Au]30}+ BF4_ in dichloromethane gives di-or trinuclear complexes of the types {(RO)2P[SAu(PR'3)]2/ 3}+/2+ (2) BF4~ as colour less, crystalline salts. As determined by single crystal X-ray diffraction studies, in the 1:2 complexes (with R = R' = Me and R' = Et, R = Ph and o-Tol), each gold atom is attached to a different sulfur atom, but with short intracationic Au-Au … Show more
“…This brings the gold and sulfur atoms closer together. An analogous packing (or no close contacts at all) has been observed with several other (Ph 3 P)AuSR‘ and (RNC)AuSR‘ complexes, generally in dimers, − whereas, for compound 1 , strings of molecules are formed, owing to the dinuclearity of the complex. 1 Molecular structure of [(Ph 3 P)Au] 2 (SSS) ( 1 ) (ORTEP drawing with 50% probability ellipsoids and H atoms omitted for clarity).…”
Section: Crystal and Molecular Structuressupporting
A series of dinuclear (phosphine)gold(I) complexes of the ambidentate 1,3,4-thiadiazoledithiolate ligand (SSS) were prepared in high yield from the corresponding (phosphine)gold(I) chlorides and K(2)(SSS) in methanol. While mononuclear components (R(3)P)AuCl with R(3) = Ph(3), Ph(2)Py, or Me(3) (1-3) gave open-chain complexes, the dinuclear components ClAu(Ph(2)P-E-PPh(2))AuCl with E = (CH(2))(6), (C(5)H(4))Fe(C(5)H(4)), or 1,4-CH(2)C(6)H(4)CH(2) afforded cyclic complexes (4-6). The products have been characterized by analytical and spectroscopic methods, and the crystal structures of 1-4 have been determined by single-crystal X-ray techniques. Crystals of 1 [(CH(2)Cl(2))(2)] and 2 (CH(2)Cl(2)) contain the molecules aggregated in strings with long and probably very weak intermolecular Au.S contacts. The P-Au-S groups are aligned parallel head-to-tail and shifted in opposite directions to reduce steric conflicts, thus ruling out aurophilic Au...Au bonding. By contrast, in crystals of 3 (CH(2)Cl(2)) with smaller tertiary phosphine ligands, the molecules are aggregated via short [3.0089(3) and 3.1048(5) A] and probably strong aurophilic bonding to give a two-dimensional network with tetranuclear units formed from four (Me(3)P)AuS moieties of four different molecules as the connecting elements. In these tetranuclear units [(Me(3)P)AuS-](4), the P-Au-S axes are rotated against each other ("crossed swords") by 108.5 degrees (P2-Au2...Au2'-P2') or 116.9 degrees (P2-Au2...Au1'-P1'), respectively, to minimize steric conflicts. There is also significant bending of the P-Au-S axes to bring the metal atoms closer together: P1-Au1-S1 = 171.88(8) degrees and P2-Au2-S2 = 165.52(8) degrees. In the crystals of the cyclic complex 4 which contain no solvent molecules, the molecular units are aggregated in strings with short closed-shell interactions between the gold atoms of neighboring molecules [3.1898(3) A]. Because of the metallocyclic structure, the shielding of the gold atoms is reduced to allow aurophilic bonding as the P-Au-S groups are rotated against each other (crossed) by a dihedral angle P-Au...Au-P of 74.6 degrees.
“…This brings the gold and sulfur atoms closer together. An analogous packing (or no close contacts at all) has been observed with several other (Ph 3 P)AuSR‘ and (RNC)AuSR‘ complexes, generally in dimers, − whereas, for compound 1 , strings of molecules are formed, owing to the dinuclearity of the complex. 1 Molecular structure of [(Ph 3 P)Au] 2 (SSS) ( 1 ) (ORTEP drawing with 50% probability ellipsoids and H atoms omitted for clarity).…”
Section: Crystal and Molecular Structuressupporting
A series of dinuclear (phosphine)gold(I) complexes of the ambidentate 1,3,4-thiadiazoledithiolate ligand (SSS) were prepared in high yield from the corresponding (phosphine)gold(I) chlorides and K(2)(SSS) in methanol. While mononuclear components (R(3)P)AuCl with R(3) = Ph(3), Ph(2)Py, or Me(3) (1-3) gave open-chain complexes, the dinuclear components ClAu(Ph(2)P-E-PPh(2))AuCl with E = (CH(2))(6), (C(5)H(4))Fe(C(5)H(4)), or 1,4-CH(2)C(6)H(4)CH(2) afforded cyclic complexes (4-6). The products have been characterized by analytical and spectroscopic methods, and the crystal structures of 1-4 have been determined by single-crystal X-ray techniques. Crystals of 1 [(CH(2)Cl(2))(2)] and 2 (CH(2)Cl(2)) contain the molecules aggregated in strings with long and probably very weak intermolecular Au.S contacts. The P-Au-S groups are aligned parallel head-to-tail and shifted in opposite directions to reduce steric conflicts, thus ruling out aurophilic Au...Au bonding. By contrast, in crystals of 3 (CH(2)Cl(2)) with smaller tertiary phosphine ligands, the molecules are aggregated via short [3.0089(3) and 3.1048(5) A] and probably strong aurophilic bonding to give a two-dimensional network with tetranuclear units formed from four (Me(3)P)AuS moieties of four different molecules as the connecting elements. In these tetranuclear units [(Me(3)P)AuS-](4), the P-Au-S axes are rotated against each other ("crossed swords") by 108.5 degrees (P2-Au2...Au2'-P2') or 116.9 degrees (P2-Au2...Au1'-P1'), respectively, to minimize steric conflicts. There is also significant bending of the P-Au-S axes to bring the metal atoms closer together: P1-Au1-S1 = 171.88(8) degrees and P2-Au2-S2 = 165.52(8) degrees. In the crystals of the cyclic complex 4 which contain no solvent molecules, the molecular units are aggregated in strings with short closed-shell interactions between the gold atoms of neighboring molecules [3.1898(3) A]. Because of the metallocyclic structure, the shielding of the gold atoms is reduced to allow aurophilic bonding as the P-Au-S groups are rotated against each other (crossed) by a dihedral angle P-Au...Au-P of 74.6 degrees.
“…Surprisingly, all attempts to poly aurate phosphine sulfides have led to a cleavage of the P−S bond after the mono auration step. In the presence of a second sulfur center, as in di thiophosph in ates, auration led to stepwise auration at each sulfur center instead of a diauration at one sulfur atom. , …”
The reaction of disodium phenyltrithiophosphonate with (triorganophosphine)gold(I) chlorides in the molar ratio
1:2 in dichloromethane gives high yields of the corresponding dinuclear complexes PhP(S)[SAu(PR3)]2 with R =
Ph (1), Me, Et, i-Pr, and o-Tol. The crystal structure of complex 1 has been determined by single crystal X-ray
methods. The two gold atoms are bound to separate sulfur atoms, leaving only one sulfur atom uncoordinated.
The compound is stabilized by an intramolecular Au···Au contact. This result shows that individual auration of
sulfur atoms is energetically preferred over double auration of only one sulfur atom. An analogous product is
obtained from trisodium tetrathiophosphate hydrate and (Ph3P)AuCl in CH2Cl2/MeOH: The reaction is accompanied
by partial methanolysis to give MeOP(S)[SAu(PPh3)]2. Again each gold atom is bound to a different sulfur atom.
In the crystal structure of this compound, intermolecular Au···Au contacts lead to one-dimensional aggregates.
All attempts to aurate the above products further with excess (R3P)AuCl or {[(R3P)Au]3O}+BF4
- reagents were
unsuccessful. P−S cleavage occurred instead to give tris[(triorganophosphine)gold)]sulfonium salts, {[(R3P)Au]3S}+X-.
The origin of this P−S cleavage has been traced by ab initio quantum chemical calculations of the mono-, bis-,
and trisauration of the model compound H3PS (phosphine sulfide) with [(H3P)Au]+ units. Only the first step was
found to be strongly exothermic (−74.5 kcal/mol), and to lead to a significant lengthening of the P−S bond. The
second step has an energy balance of only −1.1 kcal/mol, but induces a further lengthening of the P−S bond,
while the third step is strongly endothermic (+67.3 kcal/mol). Bond rupture probably sets in at the second auration
step. Quantum chemical calculations have also confirmed the experimental finding (for 1) that auration of the
dithiophosphinate anion [H2PS2]- with [(H3P)Au]+ gives the cation [H2P(SAuPH3)2]+ (with the gold atoms bound
to different sulfur atoms), the structure of which is preferred over the isomer [H2P(S)S(AuPH3)2]+ (with both
gold atoms bound to the same sulfur atom).
“…The metric parameters of the Fe 3 P 2 array are very similar to those of 3 (Table ). The P−S distance of ∼2.06 Å, Au−S distance of ∼2.31 Å, and P−Au−S bond angle of 175.7° are similar to values reported for organophosphine sulfide complexes containing P−S−Au−P interactions . The P−S−Au bond angles of 96.9° and 94.9° are slightly smaller than the values reported in the literature (96.2°−112.3°).…”
The synthesis and systematic study of the reaction chemistry of a bifunctional phosphinidene cluster,
Fe3(CO)9(μ3-PH)2 (3) is reported. Reaction chemistry at one P−H functional site is effectively communicated
through the Fe3(CO)9 core, and impacts on the reactivity of the second P−H site. Deprotonation of the acidic
protons in 3 allows access to a lone electron pair on phosphorus. The first proton is readily removed with
NEt3/[PPN]Cl ([PPN]+ = (Ph3P)2N+) to produce the [PPN]+ salt of [Fe3(CO)9(μ3-PH)(μ3-P)]- ([4]-). Removal
of both phosphorus-bound hydrogen atoms in 3 requires the use of 2 equiv of n-BuLi, to produce Li2[Fe3(CO)9(μ3-P)2] (Li2[5]). Quenching of Li2[5] with MeOH-d
4 generates [Fe3(CO)9(μ3-PD)(μ3-P)]-. The lone
electron pairs on the cluster-bound phosphorus atoms undergo analogous reaction chemistry to organophosphines.
Alkylation at the phosphorus site is carried out by reaction of [Et3NH][4] with MeOSO2CF3 generating the
monosubstituted cluster, Fe3(CO)9(μ3-PMe)(μ3-PH) (6) as the primary product. The cluster anions [4]- and
[8]-, containing a phosphorus lone pair, are oxidized by elemental sulfur to produce the phosphine sulfide
complexes, [Et3NH][Fe3(CO)9(μ3-PH)(μ3-PS)] ([Et3NH][10]) and [Et3NH][Fe3(CO)9 (μ3-PMe)(μ3-PS)] ([Et3NH][11]). Treatment of [10]- with an additional equivalent of NEt3 and S8 yields the dianionic cluster, [Et3NH]2[Fe3(CO)9(μ3-PS)2] ([Et3NH]2[12]). Without added base, reaction of the neutral clusters, 3 and 6, with
S8 in THF solution yield the clusters Fe3(CO)9(μ3-PH)(μ3-PSCH2CH2CH2CH2OH) (13), Fe3(CO)9(μ3-PSCH2CH2CH2CH2OH)2 (14), and Fe3(CO)9(μ3-PMe)(μ3-PSCH2CH2CH2CH2OH) (15), with a ring-opened THF
molecule appended to sulfur. Reaction of 3 with S8 in THF solution in the presence of ClAuPPh3 produces the
gold derivative, Fe3(CO)9(μ3-PSAuPPh3)2 (17). Like PH groups in phosphines, the μ3-PH moieties in 3 react
with activated alkenes to yield single- and double-insertion products, Fe3(CO)9(μ3-PH)(μ3-PCH2CH2R) (R =
CN (18a), CO2Me (19a)) and Fe3(CO)9(μ3-PCH2CH2R)2 (R = CN (18b), CO2Me (19b)). The solid-state
structures of 3, 17, and 18b were determined by single-crystal X-ray diffraction.
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