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Synthesis, Structure and Reactivity of PH ‐Phosphoraneiminato‐ and Iminophosphoraneiminato Group 4 Transition‐Metal Complexes
Author(s) -
Raab Michael,
Tirreé Jürgen,
Nieger Martin,
Niecke Edgar
Publication year - 2003
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.200390139
Subject(s) - chemistry , tautomer , reactivity (psychology) , transition metal , ligand (biochemistry) , metal , coordination complex , crystallography , ab initio , molecule , chemical stability , stereochemistry , computational chemistry , medicinal chemistry , organic chemistry , catalysis , medicine , biochemistry , alternative medicine , receptor , pathology
Abstract The versatile coordination chemistry of the well‐investigated phosphoraneiminato‐ligand R 3 PN — ( I ) was extended by the successive introduction of protons to the phosphorus atom. The position of the resulting equilibrium between the NH ‐phosphanylamido‐ [R 2 P‐NH — ] and the PH ‐phosphoraneiminato‐form [R 2 HP=N — ] is affected by the Lewis acidity of the coordinated metal fragment. Experimental studies on complexes with various substitution patterns at the group 4 metal center R 2 HP=N[M] ( II ) were unambiguously confirmed by DFT ‐calculations. The isolation of group 4 PH ‐dihydrido‐phosphoraneiminato‐complexes RH 2 P‐N[M] ( III ) is prevented by the low thermodynamic stability of the target molecules, also supported by the results of ab initio calculations. However, an access to the by then unknown transition‐metal substituted iminophosphanes RP=N[M] ( IV ) was verified for the first time. Within extensive studies on the coordination chemistry of bis(imino)phosphoranes RP(=NR′)(=NR″), several species of group 4 complexes R(R′N=)P=N[M] ( V ) were isolated and structurally characterized. In this case, investigations on the NH / PH ‐tautomerism were performed exclusively on theoretical level, because the required educts are experimentally non‐accessible due to their kinetic instability.