Dipalladium and diplatinum bis(µ-alkanethiolato) complexes with a planar M₂S₂ring

Platinum(II) Complexes of 2-(Dimethylamino)ethylselenolate − Donor−Acceptor Inter-Ligand Interactions as Evident from Experimental and TD-DFT Computational Analysis

“…The X-ray structures of several mononuclear compounds [M(ER) 2 (PϪP)] (E ϭ S or Se, M ϭ Pd or Pt) have been reported. [13,23] The structures reveal that in thiolates the two MϪS distances are nearly identical, [13,23] but for selenolates the two MϪSe distances differ markedly [21,23,26] (e.g. Pt-(Sepy) 2 (dppe) PtϪSe ϭ 2.498, 2.433 Å ).…”

“…The selenolato ligands form an asymmetric Pt 2 Se 2 ring [19,27] whereas the thiolates give a symmetrical Pt 2 S 2 fragment. [28] On chelation of M(ER) 2 (PϪP) with another metal centre, binuclear complexes such as [M 2 (ER) 2 (PϪP) 2 ] ϩϩ [11,13] (M ϭ Pd or Pt) are formed when E ϭ S a symmetrical M 2 E 2 bridge forms as shown by the X-ray structure of [M 2 (µ-SC 5 H 9 NMe) 2 (dppe) 2 ][BPh 4 ] 2 [13] where MϪS distances are nearly equivalent. Accordingly all phosphorus nuclei become chemically equivalent and display only one 31 P NMR resonance.…”

“…Accordingly all phosphorus nuclei become chemically equivalent and display only one 31 P NMR resonance. [11,13,21,23] In case of binuclear cationic selenolate complexes, as observed for [Pt 2 Cl 2 (µ-SeR) 2 (PR 3 ) 2 ], [19,27] the MϪSe bridge may be asymmetric (I) due to different MϪSe distances consequently making the phosphorus nuclei magnetically different. The two inequivalent phosphorus nuclei are coupled together to give doublets in the 31 P NMR spectra of 6a and 6c.…”

Homo- and hetero-, bi- and tri-nuclear palladium(II) and platinum(II) complexes containing single bridging chalcogenolate of a metallo-ligand, [MCl(ECH2CH2NMe2)(PR3)] (M=Pt, Pd; E=Se, Te)

“…complexes [1,2], self-assembled discrete two-and three-dimensional structures [3,4] and dendrimers [5]. However, bi-and tri-nuclear palladium and platinum complexes in which metal square planes linked only through a single point (A and B) are scarce and have been described recently by us [6-8] and others [9,10].The chalcogen atom in mononuclear metal chalcogenolates, cis-[M(ER 0 ) 2 (P \ P)] has been successfully employed to prepare bi-and tri-nuclear metal complexes containing ''M(l-ER 0 ) 2 M'' motif [11][12][13][14]. Thus complexes of the types, [Pt 2 (l-ER 0 ) 2 (dppm) 2 ] 2+ and [Pt 3 (l-ER 0 ) 4 (dppm) 2 ] 2+ (E = S, Se, Te) have been isolated and fully characterized [11][12][13][14].…”

Interconversion of structurally characterised complexes [PdCl(Se ̂ N)] 2 and [Pd(Se ̂ N) 2 ] 6 with the hemi-labile ligand Se ̂ N=Me 2 NCH 2 CH 2 CH 2 Se −

“…Internal functionalisation through the N donor provides a way to suppress polymerisation of metal chalcogenolates [3]. While the chemistry of mercaptoalkylamines is now fairly well explored [4][5][6], the heavier analogs containing Se or Te have been investigated only recently [1,2,[7][8][9].…”