TY - JOUR
T1 - Naphthalene and anthracene cobaltates(1-)
T2 - Useful storable sources of an atomic cobalt anion
AU - Brennessel, William W.
AU - Ellis, John E
PY - 2012/8/20
Y1 - 2012/8/20
N2 - Reductions of CoBr2 or cobaltocene by 3 equiv of potassium anthracene radical anion in tetrahydrofuran (THF) afford 60-80% yields of bis(anthracene)cobaltate(1-) (1), of interest as a readily accessible and quite labile source of spin-paired atomic Co-. Although the unsolvated potassium salt of 1 is thermally unstable at 20 °C, the [K(18-crown-6)(THF) 2]+ salt of 1 functions as a useful storable crystalline reagent for Co- in several reactions. Previously known classic cobaltates, [CoL4]-, for L = 1/2 (1,3-butadiene) (2), PF3 (3), and P(OiPr)3 (5), were obtained directly from 1 and structurally characterized for the first time. Anion 3 is noteworthy because it appears to possess the shortest known Co-P distance, av = 2.012(4) Å. Although the naphthalene analogue of 1 is not yet available as a pure substance, low-temperature reductions of CoBr2 or cobaltocene by naphthalene radical anion in the presence of 1,5-cyclooctadiene (COD) afford variable yields (80-90% from CoCp2) of (naphthalene)(COD)cobaltate(1-) (10). Ready displacement of naphthalene in 10 by L = 1,3-butadiene, 2,2'-bipyridine, and COD occurs to give good yields of the respective [Co(L)(COD)]-, all of which have been structurally characterized. Both ligands in 10 are displaced by tert-butylisocyanide to afford [Co(CNtBu)4]- (16), the first isolable and structurally characterized homoleptic alkylisocyanometalate. The molecular structure of 16 shows unprecedented bending of the isocyanides, av C-N-C = 137(2)°, for homoleptic isocyanide complexes.
AB - Reductions of CoBr2 or cobaltocene by 3 equiv of potassium anthracene radical anion in tetrahydrofuran (THF) afford 60-80% yields of bis(anthracene)cobaltate(1-) (1), of interest as a readily accessible and quite labile source of spin-paired atomic Co-. Although the unsolvated potassium salt of 1 is thermally unstable at 20 °C, the [K(18-crown-6)(THF) 2]+ salt of 1 functions as a useful storable crystalline reagent for Co- in several reactions. Previously known classic cobaltates, [CoL4]-, for L = 1/2 (1,3-butadiene) (2), PF3 (3), and P(OiPr)3 (5), were obtained directly from 1 and structurally characterized for the first time. Anion 3 is noteworthy because it appears to possess the shortest known Co-P distance, av = 2.012(4) Å. Although the naphthalene analogue of 1 is not yet available as a pure substance, low-temperature reductions of CoBr2 or cobaltocene by naphthalene radical anion in the presence of 1,5-cyclooctadiene (COD) afford variable yields (80-90% from CoCp2) of (naphthalene)(COD)cobaltate(1-) (10). Ready displacement of naphthalene in 10 by L = 1,3-butadiene, 2,2'-bipyridine, and COD occurs to give good yields of the respective [Co(L)(COD)]-, all of which have been structurally characterized. Both ligands in 10 are displaced by tert-butylisocyanide to afford [Co(CNtBu)4]- (16), the first isolable and structurally characterized homoleptic alkylisocyanometalate. The molecular structure of 16 shows unprecedented bending of the isocyanides, av C-N-C = 137(2)°, for homoleptic isocyanide complexes.
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U2 - 10.1021/ic301240u
DO - 10.1021/ic301240u
M3 - Article
C2 - 22877417
AN - SCOPUS:84865213372
VL - 51
SP - 9076
EP - 9094
JO - Inorganic Chemistry
JF - Inorganic Chemistry
SN - 0020-1669
IS - 16
ER -