Synthesis, Structural Characterization and Reactivities of (Iminophosphorano)- and (Thiophosphorano)methanide Metal Complexes

This thesis is focused in two parts: (i) the synthesis and characterization of main-group metal, transition metal and lanthanide metal complexes derived from 2-quinolyl-linked phosphoranosulfide CH2(i Pr2P=S)(C9H6N-2) ( 111) and 2,3-pyrazyl-linked bis(phosphoranosulfide) ligands {CH 2(iPr2P)}2(C 4H2N2-2,3) (113), (ii) the synthesis, characterization and reactivities of group 14 metal complexes derived from different phosphoranoimine ligands, CH2(PPh2=NSiMe 3)2 (2) and CH2(R2P=NSiMe3)(C 9H6N-2) [R = iPr ( 110a), R = Ph (110b)].;Chapter 1 describes the general aspects of phosphoranoimines and phoshoranosulfides as ligands for main group metals, transition metals and lanthanide metals. The synthesis and structural characterization of novel 2-quinolyl-linked (iminophosphorano)methane CH2(R2P=NSiMe3)(C9H6N-2) [R = iPr (110a), R = Ph ( 110b)] and (thiophosphorano)methane CH2( iPr2P=S)(C9H6N-2) ( 111), and 2,3-pyrazyl-linked (thiophosphorano)methane {CH2( iPr2P=S)}2(C4H2N 2-2,3) (113) are described.;Chapter 2 describes the synthesis and structural characterization group 13 and 14 metal complexes derived from compound 111. Deprotonation of 111 with 1 equiv of AlMe3 afforded the corresponding aluminium complex, [AlMe2{CH(iPr 2P-S) (C9H6N-2)}] (153). Furthermore, 2-quinoyl-linked thiophosphinoyl group 14 "openbox" 1,3-dimetallacyclobutane, [M{micro2-C(iPr2P=S)(C 9H6N-2)}]2 [M= Sn (155) and Pb ( 156)] can be synthesized by deprotonation of 111 with the corresponding group 14 metal(II) amide. 2-Quinolyl-linked thiophosphinoyl group 13 metal complexes [MCl2{CH(iPr 2P-S)(C9H6N-2)}] [M = Al (157) and Ga(158)], can be prepared from the metathesis reaction of the lithium complex 114 with 2 equiv of AlCl3 or GaCl 3. Metathesis reaction of the lithium complex 114 with 2 equiv of GeCl4 and SnCl4 afforded the Ge(IV) and Sn(IV) metal complexes, [MCl3{CH(iPr 2P=S)(C9H6N-2)}] [M = Ge (159), Sn (160)].;Chapter 3 describes the synthesis and structural characterization of thiophosphinoyl transition metal and lanthanide metal complexes. Metathesis reaction between lithium complex 114 with one equiv of ZrCl 4 and 1 equiv of CoCl2 afforded heteroleptic chlorozicronium(IV) and chlorocobalt(II) complexes, [ZrCl2{CH(iPr 2P=S) (C9H6N-2)}2] (201) and [CoCl{CH(iPr2P=S)2(C 9H6N-2)}]2 (202), respectively.;Chapter 4 describes the synthesis, structural characterization of group 14 metal complexes derived from 2-quinolyl-linked (iminophosphorano)methane and the reactivities of group 14 metal complexes derived from CH2(PPh 2=NSiMe3)2 (2). Compound 110b reacts with 1 equiv of GeCl2E1,4-dioxane underwent dechlorosilylation to give a dimeric heteroleptic chlorogermanium(II) complex [GeCl{CH2 (Ph2P=N) (C9H6N-2)}]2 ( 258). Compound 110a reacts with 1 equiv Pb{N(SiMe 3)2}2 afforded the "twisted-step" 1,3-diplumbacyclobutane, [Pb{micro2-C(iPr2P=NSiMe 3)(C9H6N-2)}]2 (259). Compounds 258-260, 263 have been fully characterized by elemental analysis, NMR spectroscopy and X-ray crystallography. (Abstract shortened by UMI.).