Metallaborane reaction chemistry. Part 12. Some interactions of acetylenes and isocyanides with selected metallaboranes

Reactions of small boranes with ruthenium phosphine hydrides: Oligomerisation of monoborane-tetrahydrofuran to a nido-hexaruthenaborane

“…Ten inequivalent resonances (all intensity 1) are sharpened by 11 B broad band decoupling and are assigned to the 10 hydrogen atoms of the borane cluster fragment. Interestingly, only one of the equivalent B-H-B bridging protons H (23) and H (26) shows coupling to 31 P in the PPh 3 ligands. The metal hydride H(2) is a triplet in the 1 H NMR spectrum and does not sharpen with additional 11 B decoupling.…”

A simple and high-yield route to iridium, rhodium, osmium and rutheniumnido-6-metalladecaborane compounds

“…Figure 2 is a displacement ellipsoid drawing of the molecular structure of 3 together with some selected interatomic distances and angles (for additional structural data see Table S1 in the Supporting Information, SI). Compound 3 has a basic cluster geometry that can be formally derived from the replacement of the {B6H} vertex in the ten-vertex nido-decaborane, B 10 H 14 , by a {Ru(CO)(PPh 3 ) 2 } fragment, making 3 structurally analogous to eight other nido-6-monometalladecaboranes catalogued in the Cambridge Structural Database (CSD) 16 that incorporate the metal fragments {W(H) 2 (PMe 2 Ph) 3 }, 17 {ReH(PMe 2 Ph) 3 }, 18 {Ru( 6 -C 6 Me 6 )}, 19 {Os(CO)(PPh 3 ) 2 }, 13 {Os(PMe 2 Ph) 3 }, 17 {Co( 5 -Cp*)}, 20 {Rh( 5 -Cp*)} 21 and {IrH(PPh 3 ) 2 } (1) 11 .…”

Metallaborane reaction chemistry. A predicted and found tailored facile and reversible capture of SO2 by a B-frame-supported bimetallic: structures of [(PMe2Ph)2PtPd(phen)B10H10] and [(PMe2Ph)2Pt(SO2)Pd(phen)B10H10]

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The formally closo twelve-vertex {ortho-M 2 B 10 } dimetallaborane system has been predictively tailored for reversible uptake of SO 2 across the metal-metal bond, as exemplified by the formation of [(PMe 2 Ph) 2 Pt(SO 2 )Pd(phen)B 10 H 10 ] from [(PMe 2 Ph) 2 -PtPd(phen)B 10 H 10 ].We previously demonstrated that the closo-structured twelvevertex cluster compound [(PMe 2 Ph) 4 Pt 2 B 10 H 10 ] shows a remarkable haem mimicry, in that it exhibits a readily reversible sequestration of molecular dioxygen across the intact metal-metal linkage to give [(PMe 2 Ph) 4 (O 2 )Pt 2 B 10 H 10 ]. [1][2][3] The other small unsaturated molecules SO 2 and CO are, by contrast, irreversibly sequestered to give [(PMe 2 Ph) 4 -(SO 2 )Pt 2 B 10 H 10 ] and [(PMe 2 Ph) 4 (CO)Pt 2 B 10 H 10 ], respectively. 2,3 By alteration of the metal atoms, and/or their exopolyhedral ligands and/or the boron-cluster substituents, this {M 2 B 10 } system is in principle uniquely tailorable for a variety of small-molecule sequestration, delivery, exchange and activation.

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“…[1][2][3] The other small unsaturated molecules SO 2 and CO are, by contrast, irreversibly sequestered to give [(PMe 2 Ph) 4 -(SO 2 )Pt 2 B 10 H 10 ] and [(PMe 2 Ph) 4 (CO)Pt 2 B 10 H 10 ], respectively. 2,3 By alteration of the metal atoms, and/or their exopolyhedral ligands and/or the boron-cluster substituents, this {M 2 B 10 } system is in principle uniquely tailorable for a variety of small-molecule sequestration, delivery, exchange and activation. [2][3][4] We now confirm this tailorability, with this preliminary report, of the engineering of the system by variation of two of these factors-the metallic elements used and the exopolyhedral metal ligands-to engender, now, reversibility of SO 2 sequestration.…”

“…2,3 By alteration of the metal atoms, and/or their exopolyhedral ligands and/or the boron-cluster substituents, this {M 2 B 10 } system is in principle uniquely tailorable for a variety of small-molecule sequestration, delivery, exchange and activation. [2][3][4] We now confirm this tailorability, with this preliminary report, of the engineering of the system by variation of two of these factors-the metallic elements used and the exopolyhedral metal ligands-to engender, now, reversibility of SO 2 sequestration. The direction of synthetic investigation to efficiently achieve this goal was determined by predictive DFT calculations.…”