[1‐Me‐1‐closo‐SnB₁₁H₁₁]⁻ as a potential weakly coordinating anion: Synthesis of Rh(PPh₃)₂(1‐Me‐closo‐SnB₁₁H₁₁) and comparisons with Rh(PR₃)₂ (1‐H‐closo‐CB₁₁ H₁₁)

Abstract

The closo‐stannaborane salt [Rh(PPh3)2‐(nbd)][1‐Me‐1‐closo‐SnB11H11] reacts with H2 in CH2 Cl2 solution to afford the contact ion‐pair Rh(PPh3)2(1‐Me‐closo‐SnB11H11), which has been characterized in solution and the solid state by X‐ray diffraction. © 2006 Wiley Periodicals, Inc. Heteroatom Chem 17:174–180, 2006; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20218

Chemistry of the Carba-closo-dodecaborate(−) Anion, CB11H12-

“…Increasingly, results of computations appear in experimental papers such as those on metal complexes containing derivatives of 1 , ,, and it will soon become very difficult to attempt a complete listing as we do here. After this very brief survey, we shall have an opportunity to refer to the results of ab initio and DFT calculations in more detail in appropriate locations throughout the text.…”

Stanna-closo-dodecaborate Chemistry

“…The methylated stannaborate monoanion [1-MeSnB 11 H 11 ]and the monocarbaborate monoanion [CB 11 H 12 ]are electronically isovalent heteroborate clusters and have in common the ability to coordinate to transition-metal fragments via B-H bonds. 25 What makes the stannaborate cluster unique is the stability of the dianion [SnB 11 H 11 ] 2together with its pronounced nucleophilicity at the tin vertex. Accordingly, the stannaborate cluster can also be regarded as a special tin(II) ligand.…”

“…It is important to note that the neutral closo -stannacarbaboranes Sn(CR) 2 B 4 H 4 , Sn(CMe) 2 B 9 H 9 , and the 13-vertex species Sn(CR 2 ) 2 B 10 H 10 23,24 behave as Lewis acids and react with Lewis bases to form heteroborane cages with slipped tin vertices (eq 2), while the isolobal stannaborate [SnB 11 H 11 ] 2- shows no tendency to react with Lewis bases but can readily be methylated at the tin vertex with methyl iodide (eq 3). The methylated stannaborate monoanion [1-MeSnB 11 H 11 ] - and the monocarbaborate monoanion [CB 11 H 12 ] - are electronically isovalent heteroborate clusters and have in common the ability to coordinate to transition-metal fragments via B−H bonds …”