ABSTRACT
The reagent Li[7-NHBu(t)()-nido-7-CB(10)H(12)] reacts with [Mo(CO)(6)] in NCMe at reflux temperatures, followed by addition of [N(PPh(3))(2)]Cl, to give [N(PPh(3))(2)][1,2-mu-NHBu(t)-2,2,2-(CO)(3)-closo-2,1-MoCB(10)H(10)] (1). The tungsten (2) and chromium (3) analogues were similarly obtained, but the latter is unstable and was isolated in low yield. An X-ray diffraction study of 2 confirmed that the exo-polyhedral NHBu(t) group forms a bridge between the cage-carbon atom and the tungsten. For 1, this intramolecular donor bond is lifted on protonation in the presence of donor molecules L (CO, PPh(3), PMe(3), PEt(3), PMe(2)Ph) when zwitterionic complexes [1-NH(2)Bu(t)()-2,2,2-(CO)(3)-2-L-closo-2,1-MoCB(10)H(10)] (4) are formed. In contrast, protonation with HCl gives a salt [N(PPh(3))(2)][1-NH(2)Bu(t)()-2,2,2-(CO)(3)-2-Cl-closo-2,1-MoCB(10)H(10)] (5). Complex 1 in CH(2)Cl(2) with CNBu(t) is oxidized by iodine, affording [1,2-mu-NHBu(t)()-2,2,2-(CNBu(t)())(3)-2-I-closo-2,1-MoCB(10)H(10)] (6a). Treatment of 1 with [CuCl(PPh(3))](4) in the presence of Tl[PF(6)] yields the bimetallic compound [exo-[Cu(PPh(3))]-1,2-mu-NHBu(t)-2,2,2-(CO)(3)-closo-2,1-MoCB(10)H(10)] (8), whereas reaction with [AuCl(PPh(3))] and Tl[PF(6)] affords a mixture of [1,2-mu-NHBu(t)-2-[Au(PPh(3))]-2,2,2-(CO)(3)-closo-2,1-MoCB(10)H(10)] (9) and [Au(PPh(3))(2)][2,2'-mu-Au-[1,2-mu-NHBu(t)-2,2,2-(CO)(3)-closo-2,1-MoCB(1)(0)H(10)](2)] (10a). In solution, 9 disproportionates, giving 10a. The [N(PPh(3))(2)](+) salt (10b) is readily prepared by treating 1 with [AuCl(THT)] (THT = tetrahydrothiophene) and Tl[PF(6)], and its structure was determined by X-ray diffraction.
ABSTRACT
The rhenacarborane salt Cs[Re(CO)3(eta5-7,8-C2B9H11)] (1) has been used to synthesize the tetranuclear metal complex [[ReAg(mu-10-H-eta5-7,8-C2B9H10)(CO)3]2[mu-Ph2P(CH2)2PPh2]] (3) where two [ReAg(mu-10-H-eta5-7,8-C2B9H10)(CO)3] fragments have been shown by X-ray crystallography to be bridged by a single 1,2-bis(diphenylphosphino)ethane ligand. Reaction of 1 with Ag[BF4] in the presence of the ligands bis- or tris(pyrazol-1-yl)methane yields the complexes [ReAg(mu-10-H-eta5-7,8-C2B9H10)(CO)3[kappa2-CH2(C3H3N2-1)2]] (4) or [[ReAg(mu-10-H-eta5-7,8-C2B9H10)(CO)3]2[mu-kappa1,kappa2-CH(C3H3N2-1)3]] (5), respectively. From X-ray studies, the former comprises a Re-Ag bond bridged by the carborane cage and with the bis(pyrazol-1-yl)methane coordinating the silver(I) center in an asymmetric kappa(2) mode. Complex 5 was unexpectedly found to contain a tris(pyrazol-1-yl)methane bridging two [ReAg(mu-10-H-eta5-7,8-C2B9H10)(CO)3] fragments in a kappa1,kappa2 manner. Treatment of 1 with Ag[BF4] in the presence of 2,2'-dipyridyl and 2,2':6',2' '-terpyridyl yields [ReAg(mu-10-H-eta5-7,8-C2B9H10)(CO)3[kappa2-(C5H4N-2)(2)]] (6) and [ReAg(mu-10-H-eta5-7,8-C2B9H10)(CO)3[kappa3-C5H3N(C5H4N-2)2-2,6]] (7). The X-ray structure determination of 7 revealed an unusual pentacoordinated silver(I) center, asymmetrically ligated by a kappa3-2,2':6',2' '-terpyridyl molecule. The same synthetic procedure using N,N,N',N'-tetramethylethylenediamine gave a tetranuclear metal complex [[ReAg(mu-10-H-eta5-7,8-C2B9H10)(CO)3]2[mu-Me2N(CH2)2NMe2]2] (8) which is believed, in the solid state, to be bridged between the silver atoms by two of the diamine molecules. The salt 1 with Ag[BF4] in the absence of any added ligand gave the tetrameric cluster [ReAg[mu-5,6,10-(H)3-eta5-7,8-C2B9H8](CO)3]4 (9) where, in the solid state, four [ReAg(mu-10-H-eta5-7,8-C2B9H10)(CO)3] units are held together by long interunit B-H right harpoon-up Ag bonds.
