Interpolymetallic Assembly of d⁸−d¹⁰ Sulfide Aggregates from [Pt₂(PPh₃)₄(μ-S)₂] and Group 12 Metals

Abstract

A series of heterometallic Pt-M (M=Zn and Cd) sulfide aggregates with growing nuclearities (Pt2M), (Pt4M), and (Pt4M2), viz., [ZnPt2Cl2(PPh3)4(mu3-S)2] (2), [CdPt2Cl2(PPh3)4(mu3-S)2] (3), [Pt2(PPh3)4(mu3-S)2]2[ZnSO4]2 (4), [Pt2(PPh3)4(mu3-S)2]2[CdSO4]2.H2O (5), [CdPt4(PPh3)8(mu3-S)4][ClO4]2 (7), and [ZnPt4(PPh3)8(mu3-S)4][ClO4]2 (8), have been prepared from Pt2(PPh3)4(mu-S)2 (1) with appropriate zinc and cadmium substrates. The structures have been determined by single-crystal X-ray diffraction. The supporting anions play an active role in the structural assembly process. An unexpected disintegration complex [Pt2(S2CH2)Cl(PPh3)4][PF6] (6) has also been isolated and characterized by single-crystal X-ray diffraction. The mechanism of the formation of 6 is proposed.

Synthesis and characterization of heterobimetallic complexes with pyridyl selenolato ligands. Crystal structure of [{Pt(C5H4N)(SeC5H4N)(dppp)}ZnCl2]

“…While latter resonance ~ -11 ppm with the coupling constant ~3150Hz is phenomenal agreement with reported heterometallic complexes [M{Pt2(dppe)2(μ3-S)2}X2] (M = Zn, Cd and Hg) [29,36]. Hence, this resonance belongs to selenolate ligand which is attached to platinum as well as with Cd, Hg, Cu also.…”

“…(6) -2.4919(6) Å) [40].The Pt-C (2.015(10) Å) distance is in agreement with the one reported for [PtX(Ph)(PPh3)2] (X = Cl, I) (Pt-C = 2.01(1), 2.015(9) Å) [35,36]. The Zn-N and Zn-Cl distances are as expected [29,36,[43][44][45][46].…”

“…The appearence of new resoance suggests the slowly disintigration of compound in CDCl3 solution to give an unknown moiety. This decomposition is probably facilitated by nucleophilic attack of chlorinated solvent [29]. (6) -2.4919(6) Å) [40].The Pt-C (2.015(10) Å) distance is in agreement with the one reported for [PtX(Ph)(PPh3)2] (X = Cl, I) (Pt-C = 2.01(1), 2.015(9) Å) [35,36].…”

“…The geometry around the Pt metal center is confined with 'P2Se2' fragments with distorted square planner geometry however Cd atom opts distorted octahedral shape which is defined with 'N2O2Cl' frame with Cl and Se atom at axial position. The Pt-P and Pt-Se distances are as expected [29,36] (Cd….S = 2.561(2) -2.553(2) Å) [36]. Because of these interactions Cd….Se pyridyl selenolate group move out from metal plane.…”

Inter- and hetero-metallic assembly of palladium sulfide aggregates: crystal and molecular structures of [InPd2Cl3(dppf)2(μ3-S)2]·3CH2Cl2 and [Ag2Pd2(NO3)2(dppf)2(μ3-S)2]·2CH2Cl2

“…PR3 and Me2S; X = halide or pseudohalide) react with Pt 2 L 4 (l-S) 2 to give the cooresponding d 8 -d 10 heterometallic species [14]. To verify that similar Pd(II) species can be assembled, we selected two reactions as representative studies that could give the {Pd 2 M 2 S 2 } (M = Ag (7) and Au (8)) core.…”