TY - JOUR
T1 - Synthesis, structure, spectroscopy, and reactivity of thiapentadienyl- cobalt-phosphine complexes
AU - Bleeke, John R.
AU - Lutes, Bryn L.
AU - Rath, Nigam P.
PY - 2009/8/10
Y1 - 2009/8/10
N2 - The first examples of thiapentadienyl-cobalt complexes have been synthesized and structurally characterized. Treatment of (Cl)Co(PMe 3) 3 with potassium thiapentadienide yields a dimetallic product, 1, which is held together by two bridging thiapentadienyl ligands, one of which possesses a cis internal double bond and the other a trans internal double bond. Treatment of 1 with carbon monoxide breaks apart the cluster, producing a mixture of (5-η 1-cis-5-thiapentadienyl)Co(PMe 3) 2-(CO) 2 (cis-2) and its trans isomer (trans-2). cis-2 can be made independently by reacting (Cl)Co(PMe 3) 2(CO) 2 with potassium thiapentadienide. In contrast, treatment of (Cl)Co(PMe 3) 3 with lithium 2,3-dimethyl-5-thiapentadienide generates a trimetallic product, 3. This species is held together by four bridging thiapentadienyl ligands, all possessing trans internal double bonds. In compound 3, the central cobalt is a Co(II) center, produced through a disproportionation reaction, while the two terminal cobalts are Co(I) centers. Treatment of 3 with carbon monoxide again breaks apart the cluster, producing (5-η 1-trans-2,3-dimethyl-5-thiapentadienyl) Co(PMe 3) 2(CO) 2 (trans-4). The cis isomer, cis4, can be produced by treating (Cl)Co(PMe 3) 2(CO) 2 with lithium 2,3-dimethyl-5-thiapentadienide. Compounds 1, cis-2, 3, and trans-4 have been characterized by single-crystal X-ray diffraction.
AB - The first examples of thiapentadienyl-cobalt complexes have been synthesized and structurally characterized. Treatment of (Cl)Co(PMe 3) 3 with potassium thiapentadienide yields a dimetallic product, 1, which is held together by two bridging thiapentadienyl ligands, one of which possesses a cis internal double bond and the other a trans internal double bond. Treatment of 1 with carbon monoxide breaks apart the cluster, producing a mixture of (5-η 1-cis-5-thiapentadienyl)Co(PMe 3) 2-(CO) 2 (cis-2) and its trans isomer (trans-2). cis-2 can be made independently by reacting (Cl)Co(PMe 3) 2(CO) 2 with potassium thiapentadienide. In contrast, treatment of (Cl)Co(PMe 3) 3 with lithium 2,3-dimethyl-5-thiapentadienide generates a trimetallic product, 3. This species is held together by four bridging thiapentadienyl ligands, all possessing trans internal double bonds. In compound 3, the central cobalt is a Co(II) center, produced through a disproportionation reaction, while the two terminal cobalts are Co(I) centers. Treatment of 3 with carbon monoxide again breaks apart the cluster, producing (5-η 1-trans-2,3-dimethyl-5-thiapentadienyl) Co(PMe 3) 2(CO) 2 (trans-4). The cis isomer, cis4, can be produced by treating (Cl)Co(PMe 3) 2(CO) 2 with lithium 2,3-dimethyl-5-thiapentadienide. Compounds 1, cis-2, 3, and trans-4 have been characterized by single-crystal X-ray diffraction.
UR - https://www.scopus.com/pages/publications/68149163435
U2 - 10.1021/om9004912
DO - 10.1021/om9004912
M3 - Article
AN - SCOPUS:68149163435
SN - 0276-7333
VL - 28
SP - 4577
EP - 4583
JO - Organometallics
JF - Organometallics
IS - 15
ER -