Polyhedral iridathiaborane chemistry. Reactions of nido-6-SB₉H₁₁and of [arachno-6-SB₉H₁₂]^–with [{Ir(η⁵-C₅Me₅)Cl₂}₂] to give nido-8,7-iridathiaundecarboranes. A nuclear magnetic resonance and structural study

Chemistry of 11-vertex rhodathiaboranes: reactions with monodentate phosphines

“…This conclusion is supported by comparison of the 11 B nuclear shielding patterns with that of a cluster compound of the eleven-vertex {nido-8,7-MSB 9 } configuration that does have a three-orbital cluster contribution from the metal centre, e.g. [8-(h 5 -C 5 Me 5 )-nido-8,7-IrSB 9 H 10 ] (10) 17 with an octahedral Ir(III) centre (Fig. 3, upper centre trace).…”

Effects of metal-centre orbital control on cluster character and electron distribution between borane and hydrocarbon ligands; significance of the structures of [μ-9,10-(SMe)-8,8-(PPh3)2-nido-8,7-IrSB 9H9] and [μ-9,10-(SMe)-8-(η4-C5Me5H)- nido-8,7-RhSB9H9]

“…For 2 all phenyl atoms other than the ipso-carbons have been omitted for clairty. Selected interatomic distances (Å): for 2, Ir(8)᎐P(1) 2.2916(13), Ir(8)᎐P(2) 2.3895(12), Ir(8)᎐S(7) 2.3902(14), Ir(8) ؒ ؒ ؒ S(9,10) 2.6367(14), Ir(8)᎐B(2) 2.260(5), Ir(8)᎐B(3) 2.282(5), Ir(8)᎐B(9) 2.248(6), S(9,10)᎐B(9) 2.005(7), S(9,10)᎐B(10) 1.997(6), S(7)᎐B(2) 2.064(6), S(7)᎐B(6) 1.981(6), S(7)᎐B(11) 1.912(6), B(9)᎐B(10) 1.968(9) and B(10)᎐B(11) 1.912(9): for 3, Rh(8) ؒ ؒ ؒ C(1) 2.736(2), Rh(8)᎐C(2) 2.186(2), Rh(8)᎐C(3) 2.142(2), Rh(8)᎐C(4) 2.166(2), Rh(8)᎐C(5) 2.260(2), Rh(8)᎐B(3) 2.298(3), Rh(8)᎐B(4) 2.337(2), Rh(8)᎐S(7) 2.4107(6), Rh(8)᎐B(9) 2.254(3), Rh(8) ؒ ؒ ؒ S(9,10) 2.4852(6), B(9)᎐S(9,10) 1.999(3), B(10)᎐S(9,10) 2.002(3), B(9)᎐B(10) 1.978(5) and B(10)᎐B(11) 1.940(4). For each of 2 and 3 there is little difference among the various metal-to-boron distances, emphasising the ambiguities of bonding interpretation and, in particular, the limitations of bonding models that involve or otherwise imply simplistic square-planar or octahedral models for transition-element centres…”

Metallaborane Reaction Chemistry. Part 4. Polyhedral Thiametallaborane Synthesis via Direct Incorporation of Sulfur Into Metallaboranes

“…It thereby complements the hitherto predominant route [1][2][3][4][5][6][7][8][9][10][11][12][13][14]20 that involves the converse approach, viz. the reactions of metal centres with pre-formed thiaborane substrates.…”