Synthesis, structrual characterization and reactivity of late transition metal complexes containing P,N-donor phosphine ligands

A systematic investigation on the synthesis of late transition metal complexes with P,N-donor hemilabile phosphine ligands is reported and discussed in this thesis. Seven pyridyl-phosphine, phosphino-amine and phosphino-amine ligands were used to generated nine series of late transition metal complexes which were structurally characterized by single crystal X-ray analysis. Different coordination behavior of the ligands was observed in these complexes.; The principal results obtained are as follows: (1) A non-rigid P,N-donor phosphine ligand, N-(diphenylphosphinomethyl) morpholine, was synthesized and used to synthesize a neutral tridentate organometallic ligand trans-Fe(CO)₃(Ph₂PCH₂mor)₂ which exhibits different coordination modes in generating hetero-binuclear Fe0 → Mn+ complexes (M = Hg(II), Cd(II), Cu(I)). (2) A convenient new synthesis of trans-Ru(CO) ₃(μ-L)₂{09}(L = 2-(diphenylphoshino)pyridine, N-(diphenylphosphinomethyl)morpholine) was developed. The reactions of these two tridentate organometallic ligands with selected group 11 and 12 metal salts resulted in the formation of hetero-binuclear complexes Ru0 → Mn+. (3)  N-[(diphenylphosphino)methyl]morpholine,{09}L, reacts with Na₂ PdCl₄ in dichloromethane to form (cis-Ph ₂PCH=CHPPh₂)PdCl₂, and with PdMeCl(cod) in chloroform to generate PdMeCl₂(HL) which undergoes reductive elimination and dimerization to form the binuclear Pd(I) complex Pd2Cl₂(μ-L)2. (4) The reaction of N-[(diphenylphosphino)methyl]-2-pyridinamine and N,N′-cyclohexyl[(diphenylphosphino)methyl]-2-pyridinamine with palladium(II), copper(I), and silver(I) salts and iron pentacarbonyl in different stoichiometric ratios yielded a series of complexes that display various coordination modes, including a novel P,N(amine), N(pyridyl)-bridging mode in a dinuclear silver complex consolidated by the argentophilic interaction. (5) The ligand 2,6-bis(diphenylphosphino)pyridine was used to synthesize a new neutral organometallic ligand {lcub}Fe(CO)₄{rcub} ₂(μ-L), and this Fe,N Fe-tridentate ligand reacts with silver perchlorate and mercury(II) chloride to form the corresponding hetero-polynuclear complexes. The organometallic ligand also reacts with mercury(II) acetate to form a hetero-octanuclear complex containing a square metallic core and a novel hetero-heptanuclear complex in which metal atoms are linked to form a kinky line with bends at the iron atoms. (6) The bridging ligand 2,6-bis(diphenylphosphino)pyridine, L, was used to synthesize two palladium complexes: Pd₃Cl₆(μ-L)₃ has a C₂ axis passing through an eighteen-membered macrocyclic ring; [Pd₂(μ-L)₂]2+ exhibits a rare coordination mode in which two palladium(I) atoms are each P,N-chelated by one ligand and connected to the bridging phosphorous atom of the other ligand. (7) The P,NP-tridentate ligand 2,6-bis(diphenylphosphino)pyridine, L, was employed to generate a twelve-membered metallomacrocyclic host species cis-Pt₂Me₄(μ-L)₂ that encapsulates Tl(I) and Cu(I) guest ions. The ligand was also used to synthesize another two linear heterotrinuclear complexes, [Me₂Pt(μ-L)₂Ag ₂(MeCN)₂](BF₄)₂·MeCN and [(CO) ₃Fe(μ-L)₂Ag₂(Et₂O)](ClO₄) ₂, b...