Penta- and Hexanuclear Heterometallic Carbonyl Clusters with μ₃-O Ligands

Abstract

The trigonal-bipyramidal [Fe3Au2(CO)12(PPh3)2(μ3-O)] and octahedral [Fe3Rh3(CO)15(μ3-O)]- clusters have been obtained from the reaction between a triangular [Fe3(CO)9(μ3-O)]2- cluster and metal-containing compounds Au(PPh3)X (X = Cl, NO3) and [Rh(CO)2Cl]2, respectively. X-ray structural studies revealed that the addition of two Au(PPh3) or three Rh(CO)2 groups to [Fe3(CO)9(μ3-O)]2- resulted in clusters with a virtually unchanged Fe3(μ3-O) fragment.

Crystallographic and Structural Analysis of Iron Heterometallic Compounds Part IV: Heteropentameric Compounds

“…Both contain a Fe 3 Au 2 trigonal bipyramidal moiety. The M -M bond distances differ from each other; while the mean Fe eq -Au^ bond distance in [52] of 2.734A is about 0.031 A shorter than that in [50], all remaining mean M -M bond distances are somewhat longer in [52] than those in [50]. The Fe eq -Fe eq bond distances are 2.864 (4) [53] or CIO 4 [54] anions.…”

“…The black complex [50] contains an Fe 3 Au 2 trigonal bipyramidal moiety with Au(l) and Fe (5) Structure of black (CO)9^3-S)Fe 3 Au 2 (PPh 3 ) 2 cluster [52] is similar to that of black (CO) 9 fa 3 -O)Fe 3 Au 2 (PPh 3 ) 2 [50]. Both contain a Fe 3 Au 2 trigonal bipyramidal moiety.…”

“…There are five coloured Fe 3 Au 2 complexes [50][51][52][53][54] which are the richest example in this series. The black complex [50] contains an Fe 3 Au 2 trigonal bipyramidal moiety with Au(l) and Fe (5) Structure of black (CO)9^3-S)Fe 3 Au 2 (PPh 3 ) 2 cluster [52] is similar to that of black (CO) 9 fa 3 -O)Fe 3 Au 2 (PPh 3 ) 2 [50].…”

Gold–Heterometal Interactions and Bonds

“…A structural diversity of heterodimetallic and -trimetallic cores was observed for the pentanuclear species containing Au-Fe [296][297][298][299][300][301][302][303][304][305][306][307][308][309], Au-Ru [267,272,[310][311][312][313][314][315][316][317][318][319][320][321][322][323][324][325] and Au-Os [326][327][328][329][330][331][332][333][334][335]. A (Ph 3 P)Au unit can bridge in a m 3 -fashion a face of a tetrahedral heterodimetallic (Fe 2 Ir 2 , Fe 2 Rh 2 , Ru 2 Rh 2 , Ru 3 Rh, Ru 3 Co) core [296,297,310,311,315] [311]…”

“…For Ru and Os clusters a common pattern is the edge-bridging of a (R 3 P)Au fragment to a homonuclear M 4 (M ¼ Ru [312], Os [326][327][328][329][330]) or heteronuclear M 3 W (M ¼ Ru [313], Os [331]), Ru 3 Co [315] and Os 3 Ni [332], for example, in (Ph 3 P)AuRu 3 W(h 5 -Cp)(m 3 -H)(m-H) (CO) 11 [327]. For clusters with an Au 2 M 3 core (M ¼ Fe [298][299][300], Ru [267,314,[316][317][318]) the distorted trigonal bipyramidal geometry can be considered as arising from a butterfly AuM 3 fragment m 4 -bridged by a second Au atom, for example [(Ph 3 P)Au] 2 An edge-bridged (R 3 P)Au unit was also found in pentanuclear clusters in which all four metal atoms of the butterfly tetrametallic core are coordinated by a carbon [301,302] or a nitrogen [303,321] atom. The gold atom bridges the hinge Fe-Fe or Ru-Ru bond, for example, in neutral (Et 3 P)AuFe 4 (m 4 -COMe)(CO) 12 [334,335].…”