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New evidence on the factors affecting bridging and semibridging character of carbonyl ligands. The structures of Mn 2 (CO) 7 (μ‐SCH 2 CH 2 S) and its phosphine derivatives Mn 2 (CO) 7‐X (PMe 2 Ph) X (μ‐SCH 2 CH 2 S), × = 1,2
Author(s) -
Adams Richard D.,
Kwon OSung,
Smith Mark D.
Publication year - 2002
Publication title -
israel journal of chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.908
H-Index - 54
eISSN - 1869-5868
pISSN - 0021-2148
DOI - 10.1560/2ly5-kgwm-1je1-h1h0
Subject(s) - chemistry , phosphine , ligand (biochemistry) , crystal structure , crystallography , manganese , x ray crystallography , medicinal chemistry , yield (engineering) , stereochemistry , bridging ligand , catalysis , diffraction , organic chemistry , physics , biochemistry , receptor , materials science , optics , metallurgy
The new ethanedithiolate—dimanganese carbonyl complex, Mn 2 (μ‐SCH 2 CH 2 S)(CO) 7 , 1 , was prepared in 28% yield from the reaction of 1,2,5,6‐tetrathiacyclooctane with Mn 2 (CO) 9 (NCMe). Complex 1 was characterized crystal‐lographically. It contains two Mn(CO) 3 groups joined by a Mn–Mn bond of 2.6470(6) Å in length, a dihapto ‐bridging ethanedithiolate ligand, and one strong semibridging CO ligand. The reaction of 1 with PMe 2 Ph yielded two derivatives: Mn 2 (μ‐SCH 2 CH 2 S)(CO) 6 (PMe 2 Ph), 2 , and gem ‐Mn 2 (μ‐SCH 2 CH 2 S)(CO) 5 (PMe 2 Ph) 2 , 3a , in 48% and 6% yields, respectively. When heated at 40 °C, compound 3a was transformed into three isomers, iso‐gem ‐Mn 2 (μ‐SCH 2 CH 2 S)(CO) 5 (PMe 2 Ph) 2 , 3b , 1,2‐Mn 2 (μ‐SCH 2 CH 2 S)(CO) 5 (PMe 2 Ph) 2 , 3c , and cis ‐Mn 2 (μ‐SCH 2 CH 2 S)‐(CO) 5 (PMe 2 Ph) 2 , 3d . Compounds 3b and 3c were characterized by single‐crystal X‐ray diffraction analyses. The introduction of phosphine ligand into the complexes strongly affects the semibridging character of the carbonyl ligand.