Iridium Coordination Compounds of Stanna-closo-dodecaborate

Abstract

The reaction of Vaska’s complex [IrCl(CO)(PPh3)2] with stanna-closo-dodecaborate [SnB11H11]2− (1) resulted in the formation of the trigonal bipyramidal iridium(I) compound [Ir(SnB11H11)2(CO)(PPh3)2]3− (2). In this compound, one stannaborate moiety can be readily substituted with CO or ethylene at RT and atmospheric pressure to give the trigonal bipyramidal compounds [Et4N][Ir(SnB11H11)(CO)2(PPh3)2] (3) and [Me4N][Ir(SnB11H11)(CO)(C2H4)(PPh3)2] (4). Oxidative addition of H2 was accomplished by the reaction of 2 with H2, yielding the iridium(III) compound [Et3NMe][IrH2(SnB11H11)(CO)(PPh3)2] (5), whereas the protonation of 2 resulted in the formation of [Et3NMe]2[IrH(SnB11H11)2(CO)(PPh3)2] (6). All compounds have been characterized by single-crystal X-ray diffraction analysis, multinuclear NMR spectroscopy, IR spectroscopy, and elemental analysis.

Cobalt, Rhodium, Iridium, and Ruthenium Carbonyl Complexes with Stanna-closo-dodecaborate:103Rh NMR,119Sn Mössbauer Spectroscopy, and Solid-State119Sn NMR

“…16 Three years ago we investigated the chemistry of Vaska's complex with the tin nucleophile [SnB 11 H 11 ] 2À , resulting in a trigonal-bipyramidal iridium(I) complex, [Me 4 N] 3 -[Ir(SnB 11 H 11 ) 2 (CO)-trans-(PPh 3 ) 2 ]. 11 This complex was protonated even by weak acids and undergoes oxidative addition with hydrogen. Rhodium coordination chemistry with this type of tin ligands was documented in two cases: [Cp*Rh(SnB 11 H 11 )(bipy 0 )] (bipy 0 = 4,4 0 -di-tert-butyl-2,2 0 -bipyridine) and [Bu 4 N] 2 [Rh(SnCB 10 H 11 ) 3 -trans-(PPh 3 ) 2 ].…”

“…) amount of [Rh(CO)2 Cl] 2 and 964 mg (2 mmol) of [Et 3 MeN] 2 [SnB11 H 11 ] were dissolved in 20 mL of acetonitrile. Stirring of this mixture for two hours resulted in a dark red solution.…”

1,2‐Carbagerma‐closo‐dodecaborate as a Germanium Ligand in Coordination Chemistry – Synthesis, Structure and Reactivity

“…[25] The trigonal-bipyramidal geometry in 4 is also present in the analogous stanna-closo-dodecaborate compound, [Me 4 N] 3 [Ir-trans-(PPh 3 ) 2 (CO)(SnB 11 H 11 ) 2 ], [6] the similar iridium complex [Et 4 N][Ir-trans-(PPh 3 ) 2 (CO) 2 (SnB 11 H 11 )] [6] and the rhodium complex [Bu 4 N] 2 [Rh-trans-(PPh 3 ) 2 -(SnCB 10 H 11 ) 3 ]. [11] Clearly, C behaves like D and F in favouring the equatorial positions in trigonal-bipyramidal geometries of the type ML 3 (PPh 3 ) 2 .…”

“…[2][3][4][5][6] This twelve-vertex cluster is derived from the icosahedral closo cluster [B 12 H 12 ] 2-by isolobal replacement of a BH unit with a tin atom. We have also explored the coordination chemistry of the homologous germanium di-anion, germa-closo-dodecaborate [GeB 11 H 11 ] 2-(A).…”

Bis(η2-ethylene)[azanidediylbis(diisopropylphosphine selenide)-κ2Se,Se′]iridium(III)

“…For metal complexes with [N(R 2 PQ) 2 ] À (Q = S, Se, Te) as NMR shift reagents, see: Barkaoui et al (1997). For related structures, see: Cheung et al (2006); Kirchmann et al (2008); Lundquist et al (1990); Parr et al (1999). For the C-C bond length in free ethylene, see: Stoicheff (1962).…”