Transition metal chemistry of main group hydrazides. A new long-chain diphosphine with the P[sup III]-N-N-P[sup V]-N-N-P[sup III] backbone as a chelating ligand for molybdenum, platinum, and palladium. Crystal and molecular structures of cis-[Mo(CO)[sub 4]][PhP(S) [N(Me) NHP(i-Pr)[sub 2]][sub 2]] and cis-PtCl[sub 2][PhP(S) [N(Me) NHP (i-Pr)[sub 2]][sub 2]]

The reaction of PhP(S)[N(Me)NH[sub 2]][sub 2] (1) with (i-Pr)[sub 2]PCl gave the new long-chain diphosphine ligand PhP(S)[N(Me)NHP(i-Pr)[sub 2]][sub 2] (2) in good yields. The reactions of the new ligand 2 with [Mo(CO)[sub 4](NHC[sub 5]H[sub 10])[sub 2]], PtCl[sub 2](COD), and PdCl[sub 2](PhCN)[sub 2] gave the eight-membered metallacylcic compounds cis-[Mo(CO)[sub 4]][PhP(S)[N(Me) NHP(i-Pr)[sub 2]][sub 2]] (3), cis-[PtCl[sub 2][PhP(S) [N(Me) NHP-(i-Pr)[sub 2]][sub 2]] (4), and cis-[PdCl[sub 2][PhP(S)[N(Me) NHP(i-Pr)[sub 2]][sub 2]]] (5) in good yields. The X-ray crystal structures of 3 and 4 have been determined; (3) monoclinic, space group P2[sub 1]/n, with a = 8.555(2) [angstrom], b = 19.045(2) [angstrom], c = 19.700(3) [angstrom], [beta] = 98.59(1)[degree], Z = 4, and R = 0.028; (4) monoclinic, space group P2[sub 1]/c, with a = 10.608(2) [angstrom], b = 18.714(2) [angstrom], c = 15.404(4) [angstrom], [beta] = 109.41(1)[degree], Z = 4, and R = 0.037. 22 refs., 3 figs., 5 tabs.