There is considerable current interest in the design and synthesis of new phosphorus ligands and their transition metal complexes in view of their potential applications in homogeneous catalysis. The present study is concerned with the synthesis of new chiral and achiral “ diphosphazanes”, which constitute a class of versatile short-bite bidentate phosphine ligands, and studying their reactivity towards late transition metals (Ag, Pd and Ru). Symmetrical diphosphazane ligands, MeN{P(OR)2}2 (R = (1R, 2S, 5R)-menthyl) and MeN{P(SR)2}2, (R = C6H5) and unsymmetrical diphosphazane ligands, Ph2PN(Pri)PPhY, (Y =OC6H3Me2-2,6 or NMePh) have been synthesized and structurally characterized. The reactivity of these ligands towards the transition metal precursors viz., [PdCl2(COD)] and [CpRu(PPh3)2Cl] has been investigated. The reaction of [Ru(bipy)2Cl2] with the diphosphazane, PriN(PPh2)2 in the presence of AgOTf to synthesize [Ru(bipy)2{PriN(PPh2)2}2]OTf led to an unexpected entry into the Ag(I) chemistry of this ligand. By optimizing the reaction conditions, several mononuclear, dinuclear and trinuclear complexes such as [Ag(K2-PriN(PPh2)2)2]X, [Ag(µ-PriN(PPh2)2)X]2 and [Ag3(µ-(Cl)2(µ-PriN(PPh2)2)3]X (X = NO3, OTf or PF6) have been synthesized. A polymeric complex, [Ag2(µ-PriN(PPh2)2)( µ-NO3)2]n in which the ligand adopts a unique ‘Cs’ geometry has also beenstructurally characterized. This polymeric complex is used to synthesize a helical polymer,[Ag2{µ-PriN(PPh2)2}(DABCO)(NO3)2]n and π- π stacked supramolecular assemblies such as [Ag2(NO3)2(µ-Ph2PN(Pri)PPh2)(2,2'-bipy)2] and [Ag2{µ-PriN(PPh2)2}(1,10-phen)2](NO3)2]. The reaction of a sterically bulky diphosphazane ligand, EtN{P(OC6H3(Pri)2-2,6)2}2 (L) with[(η3-1-R,R’-C3H3)Pd(µ-Cl)]2 in the presence of NH4PF6 gives the cationic complex, [(η 3-1-R,R’-C3H3)Pd(L)]PF6 (R = H; R’= H or Me) as the sole product. In the absence of NH4PF6, theinitially formed cationic complex, [(η 3-C3H5)Pd(L)]PF6 is transformed into a mixture of chlorobridged complexes over a period of 96 h. An octa-palladium complex [(η3-C3H5)(2-Cl- η3-C3H4)Pd4(µ-Cl)4(µ-L)]2 is formed as a result of nucleophilic substitution by a chloride ligand at the central allyl carbon atom. The reaction of L with [(η3-C3H5)Pd(µ-Cl)]2 in the presence of K2CO3 yields a dinuclear complex, [(η3-C3H5)Pd2(µ-L)Cl] containing a coordinatively unsaturated T-shaped palladium center. This complex exhibits high catalytic activity and large“turn-over numbers” in the catalytic hydrophenylation of norbornene. Reactions of diphosphazanes with cyclometalated palladium complexes of the general formula [Pd( k2-(C,N)-Me2NCHMe(C6H4))(solvent)2]PF6 derived from a chiral amine, (S)-N,N-dimethyl-1-phenethylamine give chelate complexes of the type [Pd{ k2-(C,N)-Me2NCHMe(C6H4)}(LL)] PF6, (L-L = diphosphazane). Chiral racemic diphosphazanes give a mixture of diastereomeric(S,R and S,S) complexes which could not be separated. These cyclometalated complexes show moderate catalytic activity in C−C bond forming reactions (hydrophenylation /Suzuki coupling).

In recent years there is an increasing awareness of the importance of chiral phosphorus ligands in transition metal organometallic chemistry because of the utility of such complexes in homogeneous catalytic reactions. This thesis deals with synthetic, spectroscopic and X-ray crystallographic studies on ruthenium complexes of chiral and achiral P-N-P type ligands, known as "diphosphazanes", with emphasis on ruthenium carbonyl clusters. Several ruthenium carbonyl clusters have been synthesized and characterized by elemental analyses, ER and NMR (lH, nC and 3lP) spectroscopic data. In several instances, the molecular structures of the clusters have been confirmed by single crystal X-ray diffraction studies. Chapter 1 provides a brief overview of various types of chiral phosphorus ligands and general synthetic routes to diphosphazanes. A brief review of the transition metal chemistry of diphosphazanes and diphosphazane chalcogenides (published since 1994) is presented A review of the literature on the carbonyl clusters of the group-8 transition metals (Fe, Ru, Os) bearing mono- and diphosphines is also included in this chapter The scope and aim of the present investigation is outlined at the end of this chapter. Chapter 2 provides the results obtained in the present investigation and a detailed discussion of the spectroscopic and crystallographic data. The essential feature of the work is summarized at the end of the chapter. Chapter 3 gives a detailed account of the experimental procedure for the synthesis of the compounds and spectroscopic and analytical measurements. The experimental details of X-ray structure determination are also given in this chapter. To save space, the coordinates of the H-atoms and the calculated and observed structure factor tables are not included. In some cases, reference to CCDC deposition number is included. The references of the literature are compiled at the end of the thesis and are indicated in the text by appropriate numbers appearing as superscripts. The compounds synthesized in the present study are represented by bold Arabic numerals and are listed in Appendix I. The abbreviations employed in the thesis conform to those generally used in Chemical Abstracts.