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The Origin of the MNXN Metallacycle Flexibility in the Chelate Iminophosphonamide and Amidinate Transition Metal Complexes
Author(s) -
Peganova Tat'yana A.,
Filippov Oleg A.,
Belkova Natalia V.,
Fedyanin Ivan V.,
Kalsin Alexander M.
Publication year - 2018
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201801119
Subject(s) - metallacycle , chemistry , palladium , ligand (biochemistry) , crystallography , platinum , metal , transition metal , stereochemistry , x ray crystallography , catalysis , organic chemistry , physics , biochemistry , receptor , diffraction , optics
A series of square planar palladium and platinum iminophosphonamides [(η 3 ‐allyl)M{Ph 2 P(N‐ p ‐C 6 H 4 R) 2 }] ( 1a–d , M = Pd; 2a , M = Pt), having N ‐aryls of various electronic properties (R = OMe, Me, i Pr, COOEt), have been synthesized and structurally characterized to reveal the correlation between the electronic properties of the N‐substituents and the geometry of the MNPN metallacycle. The experimental values of the MNPN bending angles and the pyramidalization at the N‐atoms were compared to the calculated ones for 1a – d and for the amidinate analogue [(η 3 ‐allyl)Pd{PhC(N‐ p ‐C 6 H 4 Me) 2 }] ( 7b ). A thorough analysis of the orbital interactions for both palladium iminophosphonamide and amidinates have been carried out to elucidate the effect of the ligand's central atom (C, P) on the fluxional behavior of the MNXN metallacycle and the change of its electronic structure upon bending. The conclusions derived for palladium complexes are also supported by statistical analysis of the Cambridge Structural Database for other electronically saturated metal NPN and NCN complexes.