Abstract
Abstract A review on syntheses, chemical reactions, structure and bonding of phorphoraneiminato complexes of transition metals (TM) is given. The ligand group [NPR3]−, not known as a discrete ion, is isoelectronic with, amongst others, [OSiMe3]−, and is capable of a versatile coordination chemistry. Apart from terminal functions [M]≡N–PR3 with a close to linear M–N–P axis (A) and bent axis (B), complexes with μ2-N-bridges forming symmetrical (D) or unsymmetrical (C) four-membered M2N2 rings are as well known as those of the μ3-N-type (E) leading to heterocubane M4N4 structures. The coordination type preferred is primarily dependent on the oxidation state (OS) of the TM, but also on the ligand sphere of the TM and on the steric and electronic properties of the substituents at phosphorus (R=organic group, NR′2, halogen). Types A and B are predominantly realized in complexes of metals in high OS. Electron-rich metals prefer type E, and in mediate OS bonding modes C and D prevail.
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