Palladium Chemistry with Stanna‐closo‐dodecaborate and Isocyanides

Abstract

The substitution equilibrium between isocyanides and stanna‐closo‐dodecaborate with palladium(II) was investigated. The mixed substituted products of type [(RNC)2Pd(SnB11H11)2]2– and [(RNC)Pd(SnB11H11)3]4– were characterized by X‐ray crystal structure analysis, elemental analysis and NMR spectroscopy. Isocyanide insertion into palladium–carbon bonds was also found. The zwitterionic complexes isolated from the reaction of [(P′2)Pd(Me)(SnB11H11)]– (P′2 = dppe, dppp, dppf) with isocyanides were characterized.

Germa- and Stanna-closo-dodecaborate in Reaction with [PdCl2(Xantphos)]: P–C and B–H Bond Activation

“…The shorter bond lies within the range of other published values of stanna-closododecaborate coordination at palladium. 22 The longer interatomic distance might be due to the tension inside the four-membered ring: Sn−Pd1−P1−B. The bond between the phosphorus atom and the boron atom of 1.933(5) Å can be compared with other molecules containing phosphorus connected at a borane.…”

“…12−27 Since we have already explored the reaction of palladium complexes carrying chelating phosphines such as dppp [1,3bis(diphenylphosphinopropane)] and dppe [1,2-bis-(diphenylphosphinoethane)] with the tin nuclephile [SnB 11 H 11 ] 2− , we wanted to study the influence of a phosphine with a larger bite angle on the heteroborate coordination. 22,28 In this publication we present the reaction of the two nucleophiles [EB 11 H 11 ] 2− (E = Ge, Sn) with the electrophile [PdCl 2 (Xantphos)].…”

Palladium complexes with stabilized germylene and stannylene ligands

“…The results obtained correspond to the facts found earlier. 10 In the case of the interaction of [(RNC) 2 PdCl 2 ] (R = benzyl, tert-butyl, cyclohexyl, 2,6-dimethylphenyl) with two equivalents of the tin nucleophilic [SnB 11 H 11 ] 2− species, the mixed substitution products were isolated. However, after two days there is only the tetrasubstituted complex [Et 3 MeN] 6 [Pd-(SnB 11 H 11 ) 4 ].…”

“…The volatiles from the brown filtrate were removed under vacuum to give compound 9 ( purity more than 95% (10). To a stirred solution of 7 (0.20 g, 0.29 mmol) in toluene (15 ml), GeCl 4 (0.07 ml, 0.58 mmol) was added dropwise at ambient temperature.…”

Boron, aluminium, gallium, indium and thallium

“…93 Palladium(II) adducts of stannadodecaborane have also been reported. 94 Reaction of the related germaborane system [GeB 11 H 11 ] 2À with elemental sulfur and selenium have also been described. 95 Bregadze and co-workers have reported the reaction of the 16e half-sandwich complex CpCo(S 2 C 2 B 10 H 10 )(V) with HCRC-C(O)Ph, which results in the formation of an intermediate 17e complex containing a bicyclo[2.2.1]heptene unit at the B3/B6 site of the carborane (VI).…”