Cleavage of the Se-Se bond in [2-{O(CH(2)CH(2))(2)NCH(2)}C(6)H(4)](2)Se(2) (1) and [2-{MeN(CH(2)CH(2))(2)NCH(2)}C(6)H(4)](2)Se(2) (2) by treatment with SO(2)Cl(2), bromine or iodine (1 : 1 molar ratio) yielded [2-{O(CH(2)CH(2))(2)NCH(2)}C(6)H(4)]SeX [X = Cl (3), Br (4), I (5)] and [2-{MeN(CH(2)CH(2))(2)NCH(2)}C(6)H(4)]SeI (6). The compounds were characterized in solution by NMR spectroscopy (1H, 13C, 15N, 77Se, 2D experiments). The solid-state molecular structures of 1-3, 4.HBr, 5 and 6 were established by single crystal X-ray diffraction. In all cases T-shaped coordination geometries, i.e. (C,N)SeSe (1, 2), (C,N)SeX (3, 5, 6; X = halogen) or CSeBr(2) (4.HBr), were found. Supramolecular associations in crystals based on hydrogen contacts are discussed.

The reactions of the organodichalcogenone ligands Bbit[1,1′‐(butane‐1,4‐diyl)bis(3‐methylimidazoline‐2‐thione)],Mbis [1,1′‐methylenebis(3‐methylimidazoline‐2‐selone)], Ebis [1,1′‐(ethane‐1,2‐diyl)bis(3‐methylimidazoline‐2‐selone)] and Pbis [1,1′‐(pentane1,5‐diyl)bis(3‐methylimidazoline‐2‐selone)] with gold(I/III), silver(I) and copper(I) have been studied by elemental analysis, multinuclear (1H, 13C, 19F, 31P and 77Se) NMR spectroscopy and for several products obtained the molecular structures were also established by single‐crystal X‐ray diffraction analysis. In most cases the organodichalcogenone coordinates to two metallic fragments as a bidentate bridging ligand but the ligand Mbis coordinates to silver(I) in an unprecedented tetradentate bridging‐chelate mode.

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Abstract[2‐(Me2NCH2)C6H4]SeS(S)PR2 [R = Ph (1), OiPr (2)] were prepared by reacting [2‐(Me2NCH2)C6H4]2Se2 with the appropriate disulfanes, [R2P(S)S]2. The compounds were characterized by multinuclear magnetic resonance (1H, 13C, 31P). The molecular structures of 1 and 2 were determined by single‐crystal X‐ray diffraction. Both compounds are monomeric and the nitrogen atom of the pendent CH2NMe2 arm is strongly coordinated to the selenium atom. The organophosphorus ligands are monodentate, thus resulting in a T‐shaped coordination geometry around selenium. Copyright © 2002 John Wiley & Sons, Ltd.

The reaction of [2-(Me(2)NCH(2))C(6)H(4)Se]M (M = Li, K) with the gold(phosphine) complexes [AuCl(PR(3))] gives the mononuclear gold-selenolate species [Au{SeC(6)H(4)(CH(2)NMe(2))-2}(PPh(3))] (1) or [Au{SeC(6)H(4)(CH(2)NMe(2))-2}(PPh(2)py)] (2), respectively. The treatment of the [2-(Me(2)NCH(2))C(6)H(4)Se]M with [Au(2)Cl(2)(mu-P-P)] [P-P = bis(diphenylphosphino)methane (dppm), bis(diphenylphosphino)ethane (dppe), 1,1'-bis(diphenylphosphino)ferrocene (dppf)] derivatives gives complexes with stoichiometry [Au(2){SeC(6)H(4)(CH(2)NMe(2))-2}(2)(mu-P-P)] [P-P = dppm (3), dppe (4), or dppf (5)]. These complexes exhibit a different structural framework, that is, 4 crystallizes as a chain polymer with intermolecular aurophilic bonding, while 5 shows an intramolecular Au(I)...Au(I) interaction. The gold(III) derivative Bu(4)N[Au(C(6)F(5))(3){SeC(6)H(4)(CH(2)NMe(2))-2}] (6) is obtained by reaction of [2-(Me(2)NCH(2))C(6)H(4)Se]K and Bu(4)N[AuBr(C(6)F(5))(3)], in a 1:1 molar ratio. These species exhibit luminescence which probably arises from a mixed (3)LMMCT and (3)MC excited state. The emission properties in these complexes seem to be useful for structural predictions and lead to the proposal of intermolecular aggregation in the solid state and frozen solution for complexes 1, 2, 3, whose crystal structures have not been elucidated.