Abstract
New gold(I) alkynyl metalloligands bpylCCAuL, bpyl'CCAuPPh3 , and PPN[Au(CCbpyl')2 ] (bpyl or bpyl'=2,2'-bipyridin-5-yl or -4-yl, respectively; L=PMex Ph3-x (x=1-3), P(C6 H3 Me2 -3,5)3 , PCy3 , XyNC) have been synthesized. Ligands bpylCCH and metalloligands bpylCCAuL (L=PPh3 , PMePh2 , PCy3 , CNXy) react with MX2 (M=Fe, Zn, X=ClO4 ; M=Co, X=BF4 ) to give complexes [M(bpylCCZ)3 ]X2 (Z=H or AuL). In most cases, these complexes are mixtures of fac and mer isomers in a statistical distribution, in both CH2 Cl2 and MeCN. However, for L=PPh3 , the fac isomer is dominant in MeCN. NMR and ESI-MS studies, together with the crystal structure of [Co(bpylCCAuPPh3 )3 ](BF4 )2 , suggest that this solvent dependence is originated by the formation of helical dimers between two fac complexes in MeCN. These dimers are stabilized by solvophobic effects and multiple intermolecular interactions. Complex [Fe(Ph3 PAuCCbpdiylCCAuPPh3 )3 ](ClO4 )2 (bpdiyl=2,2'-bipyridin-5,5'-diyl) was obtained by reaction of three diauro diethynylbipyridines and Fe(ClO4 )2 .
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