Synthesis and characterisation of a triple cluster of gold and boron

Abstract

Reaction of Bl0HI4 with Et3PAuMe affords the triple cluster [(H12BloA~)(A~PEt3)4(AuBloH12)], and with Cy3PAuMe (CY = cyclohexyl) the substituted complex [Cy3PAu(Bl0Hl3)] is isolated; a mechanism for the formation of the triple cluster is proposed.

Synthesis, Chemistry, and Electronic Structures of Group 9 Metallaboranes

“…The solid-state structure of 5 , shown in Figure , is very similar to [(Cp*Co) 2 B 6 H 10 ], where a μ-AuPPh 3 unit replaces one M–H–B proton. The average Co–B bond lengths are comparable to previously reported hydride compounds. , Similarly, the average Au–B bond lengths are comparable to other reported aurated polyboranes . [Au­(PPh 3 )] moiety is bonded to 4 in μ 3 fashion that resembles the bonding mode of Au in [{(H 11 C 6 ) 3 PAu} 2 B 8 H 10 ], [11- endo -{Au­(PPh 3 )}-7,9-Me 2 - nido -7,9-C 2 B 10 H 10 ]and [(Cp*Rh) 2 (AuPPh 3 ) 2 B 6 H 8 ] (Chart ) where gold represents a vertex of the polyhedron.…”

“…Although numerous transition-metal derivatives of boranes are known for a variety of metal atoms, only few examples are known that involve Group 11 elements (Cu, Ag, and Au). − Several decaborane-14 have been transformed into mono- and diaurated boranes via metathesis with [(R 3 P)­AuMe] complexes (R = Cy, o-Tol, PPh 3 , etc. ). − Recently, we have also isolated a few rhodium gold borane complexes from the reaction of [(Cp*Rh) 2 B 6 H 10 ] or [(Cp*Rh) 2 B 8 H 12 ] with [Au­(PPh 3 )­Cl] (Chart ). These results from our work and others, − encouraged us to explore the same with the iridium system as both Rh and Ir being from the same group are expected to follow a similar reactivity trend.…”

“…). − Recently, we have also isolated a few rhodium gold borane complexes from the reaction of [(Cp*Rh) 2 B 6 H 10 ] or [(Cp*Rh) 2 B 8 H 12 ] with [Au­(PPh 3 )­Cl] (Chart ). These results from our work and others, − encouraged us to explore the same with the iridium system as both Rh and Ir being from the same group are expected to follow a similar reactivity trend. Thus, we performed the reaction of 1 with [Au­(PPh 3 )­Cl] with an excess of sodium hydride.…”

Gold–boron chemistry. Part 2. The interaction of {AuP(C6H11)3} bridges with decaboranyl cages: the accurate structure of [5,6-µ-{AuP(C6H11)3}-nido-B10H13], and the synthesis and molecular and electronic structures of its conjugate base [5,6,9,10-µ4-{AuP(C6H11)3}-nido-B10H12]–

“…(la") and second and third h.o.m.0.s (la' and 2a') of (111) by virtue of non-zero overlaps with acceptor orbitals on (IV) that are yz-noded components of e pairs and a, orbitals respectively, and the relative extents of these interactions determine the formal co-ordination geometry of the gold atom in the product (V). Because of the large number of (especially) potential acceptor orbitals of suitable symmetry, we find that interpretation of interfragment overlap integrals is [(B10H12)Au(B10H1 2)1- 28 and C(B10H12Au)(AuPR3)4- largely unhelpful in analysing the bonding in (V). However, examination of the occupations of formerly filled fragment m.0.s in (V) is more rewarding.…”

Gold–boron chemistry. Part 1. Synthetic, structural, and spectroscopic studies on the compounds [5,6-µ-(AuPR3)-nido-B10H13](R = cyclo-C6H11or C6H4Me-2)

“…Similar reactions using [AuCI(PPh,)] and [AuCl(PEt,)] did not afford analogues of (1) in detectable amounts, but instead produced orange-yellow compounds which are currently being studied. 44 The isolation of compounds (la) and (lb) from B,,H,, and We are actively pursuing alternative routes to these analogues that d o not allow their further reaction.…”