Synthese und Struktur chiraler Heterometallatetrahedrane des Typs [Re₂(M¹PPh₃)(M²PPh₃)(μ‐PCy₂)(CO)₇C≡CPh] (M¹ = Ag, Au; M² = Cu, Ag, Au)

Abstract

Syntheses and Structure of Chiral Metallatetrahedron Complexes of the Type [Re2(M1PPh3)(M2PPh3)(μ‐PCy2)(CO)7C≡CPh] (M1 = Ag, Au; M2 = Cu, Ag, Au) From the reaction of Li[Re2(μ‐H)(μ‐PCy2)(CO)7(C(Ph)O)] (1) with Ph3AuC≡CPh both benzaldehyde and the trinuclear complex Li[Re2(AuPPh3)(μ‐PCy2)(CO)7C≡CPh] (2a) were obtained in high yield. The complex anion was isolated as its PPh4‐salt 2b. The latter reacts with coinage metal complexes PPh3M2Cl [M2 = Cu, Ag, Au] to give chiral heterometallatetrahedranes of the general formula [Re2(AuPPh3)(M2PPh3)(μ‐PCy2)(CO)7C≡CPh] (M2 = Cu 3a, Ag 3b, Au 3c). The corresponding complex [Re2(AgPPh3)2(μ‐PCy2)(CO)7C≡CPh] (3d) is obtained from the reaction of [Re2(AgPPh3)2(μ‐PCy2)(CO)7Cl] (4) with LiC≡CPh. 3d undergoes a metathesis reaction in the presence of PPh3CuCl giving [Re2(AgPPh3)(CuPPh3)(μ‐PCy2)(CO)7C≡CPh] (3e) and PPh3AgCl. Analogous metathesis reactions are observed when 3c is reacted with PPh3AgCl or PPh3CuCl giving 3a or 3b, respectively. The reaction of 1 with PPh3AuCl gives benzaldehyde and Li[Re2(AuPPh3)(μ‐PCy2)(CO)7Cl] (5a) which upon reaction with PhLi forms the trinuclear complex Li[Re2(AuPPh3)(μ‐PCy2)(CO)7Ph] (6a). Again this complex was isolated as its PPh4‐salt 6b. In contrast to 2b, 6b reacts with one equivalent of Ph3PAuCl by transmetalation to give Ph3PAuPh and PPh4[Re2(AuPPh3)(μ‐PCy2)(CO)7Cl] (5b). The X‐ray structures of the compounds 3a, 3b, 3e and 4 are reported.

Copper(I) Alkyne and Alkynide Complexes

“…As an example, the reaction of [CuCCPh­(PPh 3 )] with [Ru 3 (μ-H) 3 (μ 3 -CBr)­(CO) 9 ] afforded the cluster [Ru 3 (μ-H) 3 (μ 3 -CCCPh)­(CO) 9 ]. Trinuclear clusters featuring a [MCCPh] unit (M = Cu, Ag, Au) are chiral heterometallatetrahedranes of the type [Re 2 (AuPPh 3 )­(MPPh 3 (μ-P­(C 6 H 11 ) 2 )­(CO) 7 CCPh] ( 8 ) . The respective copper alkynides could be prepared by consecutive synthetic methodologies, including the addition of LiCCPh to [Re 2 (AuPPh 3 ) 2 (μ-P­(C 6 H 11 ) 2 )­(CO) 7 Cl] to afford [Re 2 (AuPPh 3 ) 2 (μ-P­(C 6 H 11 ) 2 )­(CO) 7 CCPh], which undergoes a metathesis reaction in the presence of [CuCl­(PPh 3 )], giving upon concomitant precipitation of [AgCl­(PPh 3 ] the title complex 8 .…”

“…Trinuclear clusters featuring a [MCCPh] unit (M = Cu, Ag, Au) are chiral heterometallatetrahedranes of the type [Re 2 (AuPPh 3 )(MPPh 3 (μ-P(C 6 H 11 ) 2 )(CO) 7 CCPh] (8). 55 The respective copper alkynides could be prepared by consecutive synthetic methodologies, including the addition of LiCCPh to [Re 2 (AuPPh 3 ) 2 (μ-P(C 6 H 11 ) 2 )(CO) 7 Cl] to afford [Re 2 (AuPPh 3 ) 2 (μ-P(C 6 H 11 ) 2 )(CO) 7 CCPh], which undergoes a metathesis reaction in the presence of [CuCl-(PPh 3 )], giving upon concomitant precipitation of [AgCl-(PPh 3 ] the title complex 8. The molecular structure of this cluster in the solid state was determined by single-crystal X-ray structure analysis, as shown in Figure 4.…”

“…The molecular structure of this cluster in the solid state was determined by single-crystal X-ray structure analysis, as shown in Figure 4. 55 Other phosphine-stabilized copper phenylacetylide complexes are mononuclear [CuCCPh(C 5 H 3 N-2,6-(CH 2 P t Bu) 2 )] (9) and dimeric [Cu(μ-CCPh)(2-CH 2 P t Bu-6-Me-C 5 H 3 N)] 2 (10), of which the latter species was characterized by a single-crystal X-ray structure determination. 56 The geometry around copper in 10 is distorted tetrahedral.…”

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 …”

“…The shortest Au-Cu distances within the cluster cation are 3.216(4) and 3.376(4) Å, which indicates weak Au III -Cu I interactions. Trimetallic clusters with tetrahedral AuRe 2 Cu [201,202] or capped-trigonal bipyramidal AuRu 4 Cu [345,346] skeletons have also been reported. Examples are [(Ph 3 P) Au][(Ph 3 P)Cu]Re 2 (m-PCy 2 )(CO) 7 (C:CPh) 167 [Au-Cu 2.644(2) Å] [201] or (m-dppe) AuRu 4 Cu(m 3 -H) 2 (CO) 12 231 [Au-Cu 2.614(2) Å] [345].…”