Bimetallic alkoxysilyl complexes with bis(diphenylphosphino)methane, 2-(diphenylphosphino)pyridine or (diphenylphosphino)acetophenone ligands: crystal structure of [Fe{μ-Si(OMe)2(t(CNR)][PF6] (R = 2,6-xylyl)

Abstract The heterobimetallic carbene complexes [Fe{μ-Si(OMe) 2 ( OMe)}(CO) 3 (μ-dppm)P t{ C(CH 2 ) 2 CH(R)O }] [PF 6 ](R  H ( 2a ), Me ( 2b )) and isonitrile complexes [Fe{μ-Si(OMe) 2 ( OMe)}(CO) 3 (μ-dppm)P t(CN R][PF 6 ] (R = 2,6-xylyl ( 3a ), or t -butyl ( 3b )) have been prepared by the reaction of [Fe{μ-Si(OMe) 2 ( OMe)}(CO) 3 (μ-dppm)P tCl] with 3-butyn-1-ol or (±)-4-pentyn-2-ol or RNC respectively, in the presence of TIPF 6 . The (trimethoxy) silyl ligand bridges the two metals, as a result of a SiO→Pt interaction. The structure of 3a was refined to R = 0.029 and R w = 0.041 on the basis of 5764 reflections having F 0 2 > 3σ( F 0 2 ). Upon reaction of cis -[ MCl{(PhO) 2 P(OC} 6 H 4 )}{P(OPh) 3 }](M  Pt ( 5a ), or Pd ( 5b ) with K[Fe{Si(OMe 3 })(CO) 3 (η 1 -dppm)](K 1a ) the ortho -metallated heterobimetallic complexes cis -[Fe{Si(OMe) 3 })(CO) 3 (μ-dppm) Pt{P(OPh) 2 (OC 6 H 4 )}] ( 6a ) and trans -[Fe{Si(OMe) 3 }(CO) 3 (μ-dppm) Pd{P(OPh) 2 (OC 6 H 4 )}] ( 6b ) were formed. The phosphinopyridine- and ketophosphine-bridged complexes [Fe{Si(OMe) 3 }(CO) 3 (μ-Ph 2 Ppy)Pd(8-mq)] ( 8 ) and [Fe{Si(OMe) 3 }(CO) 3 {μ-Ph 2 PCH 2 C( O)Ph}P) d(8-mq)] ( 10 ) are described. We also discuss the preparation, dynamic behaviour and spectroscopic properties of heterobimetallic allyl-type complexes ([Fe{Si(OMe) 3 }(CO) 3 (μ-dppm)Ni(μ 3 -C 3 H 5 )] ( 11 ), [Fe{Si(OSiMe 3 ) 3 } (CO) 3 (μ-dppm)Pd(η 3 -C 3 H 5 )] ( 12a ), [Fe{SiMe(OSiMe 3 ) 2 }(μ-dppm)Pd(η 3 -C 3 H 5 )] ( 12b ), [Fe{Si (OMe) 3 }(CO) 3 (μ-Ph 2 Ppy)Pd(η 3 -RC 3 H 4 )] (R  H ( 13a ) or Me ( 13b )) and [Fe{Si(OMe) 3 }(CO) 3 - (μ-dppm)Pt(η 3 -C 8 H 13 )] ( 14 )). Treatment of [NiCp(PPh 3 )Br] with [NEt 3 H] 1a yielded the heterobimetallic complex [Fe{Si(OMe) 3 } (CO) 3 (μ-dppm)NiCp] ( 15 ).