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Polyhedral Molybdenaborane Chemistry: nido ‐6‐molybdenadecaboranes including the molecular structure of [6,6,6,6‐(CO) 2 (PMe 2 Ph) 2 ‐ nido ‐6‐MoB 9 H 12 ‐5‐Cl] Some Structural Intercomparisons
Author(s) -
Greenwood N. N.,
Kennedy J. D.,
Macpherson I.,
ThorntonPett M.
Publication year - 1986
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.19865400908
Subject(s) - monoclinic crystal system , rhenium , chemistry , osmium , crystallography , ruthenium , crystal structure , heteroatom , metal , x ray crystallography , stereochemistry , diffraction , inorganic chemistry , ring (chemistry) , physics , biochemistry , organic chemistry , catalysis , optics
Abstract The new ten‐vertex‐ nido ‐metallaborane clusters [6,6,6,6‐(CO) 2 (PPh 3 ) 2 ‐6‐MoB 9 H 13 ] 1 , [6,6,6,6‐(CO) 3 (PMe 2 Ph)‐6‐WB 9 H 13 ] 2 , and [5‐Cl–6,6,6,6‐(CO) 2 (PMe 2 Ph) 2 ‐6‐MoB 9 H 12 ] 3 have been prepared and characterized by multielement n.m.r. spectroscopy ( 1 H, 11 B, and 31 P). The fluxional properties of the exopolyhedral ligands on the metal centres have also been studied, leading to activation energies ΔG≠ (at the coalescence temperature) of 44 ± 2 kJ mol −1 (at −34°C) for 1 and 52 ± 2 kJ mol −1 (at 6.5°C) for 3 . The detailed structure of 3 has been established by single‐crystal X‐ray diffraction analysis using 3350 “observed” reflections and 337 parameters (R = 0.0268, R′ = 0.0299). The monoclinic crystals have a = 1590.3(2), b = 1028.4(2), and c = 1696.4(1) pm, β = 94.30(1)°, space group P2 1 /c and Z = 4. The results allow comparison with other previously synthesized nido ‐6‐metalladecaborane clusters in which the heteroatom is tungsten, rhenium, osmium, or ruthenium.