Ruthenium(II), copper(I) and silver(I) complexes of large bite bisphosphinite Ph 2 P{(-OC 10 H 6 )(μ-CH 2 )(C 10 H 6 O-)}PPh 2 (1) are described. Reactions of bisphosphinite 1 with [Ru(η 6 -p-cymene)(μ-Cl)Cl] 2 and RuCl 2 (PPh 3 ) 3 afford mono- and bis-chelate complexes [RuCl(η 6 -p-cymene){η 2 -Ph 2 P{(-OC 10 H 6 )(μ-CH 2 )(C 10 H 6 O-)}PPh 2 -κP,κP}]Cl (2) and trans-[RuCl 2 {η 2 -Ph 2 P{(-OC 10 H 6 )(μ-CH 2 )(C 10 H 6 O-)}PPh 2 -κP,κP} 2 ] (3), respectively. Treatment of 1 with CuX (X=Cl, Br and I) furnish 10-membered chelate complexes of the type [Cu(X){η 2 -Ph 2 P(-OC 10 H 6 )(μ-CH 2 )(C 10 H 6 O-)PPh 2 -κP,κP}] (4, X=Cl; 5, X=Br; 6, X=I), whereas [Cu(MeCN) 4 ]PF 6 affords a bis-chelated cationic complex [Cu{η 2 -Ph 2 P(-OC 10 H 6 )(μ-CH 2 )(C 10 H 6 O-)PPh 2 -κP,κP} 2 ][PF 6 ] (7). Reaction between 1 and AgOTf produce both mono- and bis-chelated complexes [Ag{η 2 -Ph 2 P(-OC 10 H 6 )(μ-CH 2 )(C 10 H 6 O-)PPh 2 -κP,κP}(SO 3 CF 3 )] (8) and [Ag{η 2 -Ph 2 P(-OC 10 H 6 )(μ-CH 2 )(C 10 H 6 O-)PPh 2 -κP,κP} 2 ][SO 3 CF 3 ] (9), respectively; whereas the similar reaction of 1 with[Ag(OTf)PPh 3 ] affords chelate complex of the type [Ag{η 2 -Ph 2 P(-OC 10 H 6 )(μ-CH 2 )(C 10 H 6 O-)PPh 2 -κP,κP}(PPh 3 )(SO 3 CF 3 )] (10). All the complexes were characterized by 1 H NMR, 31 P NMR, elemental analysis and mass spectrometry, including low-temperature NMR studies in the case of silver complexes. The molecular structures of 4 and 6 are determined by X-ray diffraction studies. Ruthenium complexes 2 and 3 promote catalytic hydrogenation of styrene and phenylacetylene with good turnover numbers.