Stepwise Synthesis of the Functionalized Metallatetrahedron Re₂(AuPPh₃)₂(μ-PCy₂)(CO)₇X (X = Cl, Br, I)

Abstract

In THF solution the dirhenium complex Re 2 (µ-H)(µ-PCy 2 )(CO) 8 (1) reacts with an equimolar amount of LiPh at -100°C to afford after warming up to room temperature within 1 h the salt Li[Re 2 (µ-H)(µ-PCy 2 )(C(Ph)O)-(CO) 7 ] (Li[2]). Through cation exchange of Li + against PPh 4 + , Li[2] gives the airstable solid PPh 4 [2] in 86% yield. The selectivity of the LiPh attack at one of the four axial carbonyls in 1 was proved by the chiral shift reagent Eu(hfac) 3 which was dissolved in a CDCl 3 solution of PPh 4 [2]. The 1 H and 31 P NMR spectra show the diastereomeric resolution of the respective peaks in an integral ratio of 1:1 e.g. ∆δ(µ-P) 0.43. The anion [2 -] generates with 2 equiv of XAuPPh 3 (X ) Cl, Br, I) in THF at room temperature within 15 min under release of the leaving group PhCHO the yellow cluster complexes Re 2 (AuPPh 3 ) 2 (µ-PCy 2 )(CO) 7 X (4a-c). Their precursor complex anions [Re 2 (µ-AuPPh 3 )(µ-PCy 2 )(CO) 7 X] -(3a-c) are obtained from 1 and an equimolar amount of XAuPPh 3 or from the deauration by treatment of 4a (X ) Cl) with 1 equiv of LiPh via a transmetalation reaction. Such anions are isolable as salts, N(PPh 3 ) 2 [3a-c]. All new cluster complexes are identified by means of 1 H NMR, 31 P NMR and ν(CO) IR spectroscopic measurements, Li[2] and 4a (X ) Cl) additionally by means of X-ray single-crystal structure analyses. Li[2] crystallizes triclinic, space group P1 h, Z ) 2, a ) 10.536(2) Å, b ) 11.433(2) Å, c ) 19.125(3) Å, R ) 98.01(1)°, ) 89.94(1)°, and γ ) 112.22(1)°; 4a crystallizes monoclinic, space group P2 1 /c, with Z ) 4, a ) 18.615(5) Å, b ) 13.606 (2) Å, c ) 24.223(6) Å, and ) 105.14(2)°. The molecular structure of Li[2] shows a µ-H-, µ-P-bridged Re-Re bond of 3.1667(7) Å, the one of 4a a tetrahedrally shaped Re 2 Au 2 core with a µ-P-bridged Re-Re edge of 3.2680(10) Å.

Synthesis and Characterization of Manganese(I) Carbonyl Complexes of the Type [(OC)4Mn{μ‐P(R)Aryl}]2

“…Thus, the short bonds are observed to the bridging PH 2 [21] and PMe 2 [22] ligands, whereas the large Mn-P distances are enforced by the rather demanding P(cHex) 2 [9] and P(C 6 H 3 -3,5-Me 2 ) 2 groups. The shape of the central four-membered Mn 2 P 2 ring also is influenced by the steric demand of the bridging phosphanide ligands with larger P-Mn-P bond angles for www.zaac.wiley-vch.de bulky phosphanides.…”

“…Metalation of these secondary phosphanes with Mn 2 (CO) 10 in boiling xylene (mixture of isomers) till the evolution of gaseous carbon monoxide ceased gave the dinuclear complexes of the type [(OC) 4 Mn{μ-P(R)Aryl}] 2 with poor to moderate yields (Scheme 3) in analogy to an earlier procedure. [9] These manganese(I) complexes are only sparingly soluble or even nearly insoluble in hydrocarbons at room temperature. Therefore, no reliable NMR spectroscopic data were obtained for compound 6.…”

“…[4] (iv) The addition of phosphanes to manganese carbonyl also allowed the isolation of [(OC) 4 Mn{μ-PRRЈ}] 2 (R, RЈ = H, Ph, Me, cHex) with rather poor yields. [6][7][8][9] The reaction of Mn 2 (CO) 10 with H 2 P-cHex gave desired [(OC) 4 Mn{μ-P(H)cHex}] 2 with a yield of 10.5 % and the side-product [{(OC) 4 Mn} 2 {μ-P(H)cHex}(μ-H)] with a yield of 40.8 %. [8] (v) The reduction of R 2 P(S)-P(S)R 2 with Mn 2 (CO) 10 yielded a mixture of [(OC) 4 Mn{μ-PR 2 }] 2 and [(OC) 3 Mn(μ-S=PR 2 )] 3 (R = Me, Et, nPr, nBu).…”

Gold–Heterometal Interactions and Bonds

“…Most of them contain tetrahedral AuRe 3 [199,200] or AuRe 2 M (M¼ Cu, Ag) [194,201,202], Au 2 Mn 2 [180], Au 2 Re 2 [190,194,[202][203][204][205] and Au 3 Re [188] skeletons …”

Selektive Darstellung zweifach diorganophosphido-verbrückter Metallatetrahedrane [Re2(MPR3)2(μ-PR2)2(CO)6] mit Re2M2-Metallgerüst (M = Au, Ag)

“…Wir berichten nachfolgend u È ber ein mehrstufiges Syntheseverfahren zu den neuen Titelverbindungen, ausgehend von dem in unserem Arbeitskreis fru È her dargestellten Salz Li[Re 2 (AuPR' 3 )(l-PR 2 )(CO) 7 Cl] (R = Cy, R' = Ph) [2].…”