Group VI metal complexes of tris(diphenylphosphinomethyl)phenylborate: modulation of ligand donation via coordination of M(CO)3 units at the borate phenyl substituent

摘要: A series of d6 metal complexes tris(diphenylphosphinomethyl)phenylborate ([PhB(CH2PPh2)3]−, PhBP3), including [Et4N][M(CO)3(PhBP3)] (M = Cr, Mo, W), inaugural group VI tris(phosphino)borate complexes, and zwitterionic Mn(CO)3(PhBP3) have been synthesized fully characterized. An analysis IR ν(CO) data for indicates that PhBP3 is significantly less strongly donating than Tp towards zerovalent M(CO)3 fragments; does not function as a scorpionate in this system its cationic fragments suggesting may an effective surrogate hydrotris(1-pyrazolyl)borate metals. While the centers are very likely still more electron-rich those M(CO)3(triphos), anions do provide robust oxidative addition products analogous to M(CO)3(triphos). new bi-functional role was investigated via synthesis seven structurally characterized bimetallics which monovalent [Mn(CO)3]+ bind three phosphine atoms borate phenyl substituent. support modest attenuation donor ability at phosphorus upon η6-phenyl substituent binding, representing inductive strategy tuning tris(phosphino)phenylborate donation κ3-phosphine-bound fragment.