Structural, Theoretical, and Spectroscopic Study of Mercury(II) Complexes of two New Unsymmetric Phosphorus Ylides

Abstract

The reaction of Ph2PCH2PPh2 (dppm) with 4-methylphenacyl bromide and 2-(bromoacetyl)naphthalene in chloroform produce the new phosphonium salts [Ph2PCH2PPh2CH2C(O)C6H4Me]Br (1) and [Ph2PCH2PPh2CH2C(O)C10H7]Br (2). Further, by reaction of the monophosphonium salts of dppm with the strong base Et3N the corresponding bidentate phosphorus ylides, Ph2PCH2P(Ph)2 = C(H)C(O)C6H4Me (3) and Ph2PCH2P(Ph)2 = C(H)C(O)C10H7 (4) were obtained. The reaction of these ligands with mercury(II) halides in dry methanol led to the formation of the mononuclear complexes {HgX 2[(Ph2PCH2PPh2C(H)C(O)C6H4Me)]} [X = Cl (5), Br (6), and I (7)] and {HgX 2[(Ph2PCH2PPh2C(H)C(O)C10H7)]} [X = Cl (8), Br (9), and I (10)]. Characterization of the obtained compounds was performed by elemental analysis, IR, 1H, 31P, and 13C NMR spectra. The structure of compounds 3 and 10 are unequivocally determined by single crystal X-ray diffraction techniques. X-ray analysis of 10 reveals the presence of mononuclear complex containing Hg atom in a distorted tetrahedral environment. In all complexes, the title ylides are coordinated through the ylidic carbon and the phosphine phosphorus. Computational studies on ligand 4 and complexes 8, 9, and 10 at DFT (B3LYP) level of theory are also reported. It was shown that the formation of P,C-coordinated 1+1 complex 10 is energetically more favored than corresponding P,P-coordinated 1+2 product. [Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the following free supplemental files: Additional figures]