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Reactions of [Cu(CH(3)CN)(4)]X (X = PF(6), BF(4)) with bis(diphenylphosphino)methane (dppm = Ph(2)PCH(2)PPh(2)) and ammonium dialkyldithiophosphates, (NH(4))[S(2)P(OR)(2)] (R = Et, (i)Pr), yield a series of novel Cu(I) polynuclear complexes, trinuclear [Cu(3)(mu-dppm)(3)(mu(3)-Cl){S(2)P(OEt)(2)}] (PF(6)) 1 and [Cu(3)(mu-dppm)(2){S(2)P(OR)(2)}(2)](PF(6)) (R = Et, 2; (i)Pr, 3), tetranuclear [Cu(4)(mu-dppm)(2) {S(2)P(OEt)(2)}(4)] 4, and hexanuclear [Cu(6)(mu-dppm)(2)(mu(4)-Cl){S(2)P(O(i)()Pr)(2)}(4)](BF(4)) 5. Similarly, the reaction of [Cu(2)(mu-L-L)(2)(CH(3)CN)(2)](PF(6))(2) (L-L, dppm, dppe = Ph(2)PCH(2)CH(2)PPh(2)) with (NH(4))[S(2)P(OR)(2)] yields dinuclear [Cu(2)(mu-dppm)(2){S(2)P(OR)(2)}(2)] 6 (R= (i)Pr, 6A; Et, 6B), trinuclear [Cu(3)(mu-dppe)(3)(mu-Cl)(2){S(2)P(O(i)Pr)(2)}] 9, and polymeric [Cu(mu(2)-dppe){S(2)P(OR)(2)}](n) (R = Et, 7; (i)Pr, 8) complexes. The formation of 1 and 5 involved the abstraction of chloride from dichloromethane when the Cu/S(2)P(OR)(2) ratio exceeded 1, but when ratio was 1:1, no Cl abstraction occurred, as in compound 4. Compound 9, however, was obtained as a 12% byproduct in the synthesis of 8 using a 1:1:1 ratio of Cu/dppe/S(2)P(O(i)Pr)(2). The chloride binds to Cu atoms in a mu(3)-Cl mode by capping one face of the Cu(3) triangle of cluster 1. A mu(4)-Cl caps a single tetragonal face of the trigonal prism of cluster 5, and in the cluster 9, two chlorides bond in mu(2)-Cl modes. Both clusters 2 and 3 exhibit the mu(3)-S mode of bonding for dtp ligands. Only cluster 5 exhibited close Cu...Cu contacts (2.997-3.0238 A). All of compounds were characterized by single-crystal X-ray diffraction and pertinent crystallographic data for 1, 5, and 9 are are follows: (1) C(79)H(76)ClCu(3)F(6)O(2)P(8)S(2), triclinic, P, a = 11.213(1) A, b = 14.142(1) A, c = 25.910(2) A, alpha = 95.328(2) degrees , beta = 99.594(2) degrees , gamma = 102.581(2) degrees , V = 3918.2(6) A(3), Z = 2; (5) C(74)H(100)BClCu(6)F(4)O(8)P(8)S(8), monoclinic, P2(1)/n, a = 25.198(4) A, b = 15.990(3) A, c = 25.421(4) A, beta = 106.027(3) degrees , V = 9845(3)A(3), Z = 4; (9) C(84)H(86)Cl(2)Cu(3)O(2)P(7)S(2), monoclinic, C2/c, with a = 24.965(3) A, b = 17.058(2) A, c = 20.253(2) A, beta = 95.351(4) degrees , V = 8587.4(17)A(3), Z = 4.

Treatment of [Zn(tmeda)Cl2] (tmeda = N, N, N', N'-tetramethylethylenediamine) with a phosphonate-substituted 2-cyanoethylene-1,1-dithiolato ligand in air yields a tetranuclear zinc-carbonate complex 1 having the formula of [Zn4(tmeda)3(mu3-CO3){S2CC(CN)P(O)(OEt)2}3] in which four zinc atoms form a trigonal pyramid with the apical zinc atom in a hitherto unknown S3O3 coordination sphere. It is the first example of aerial CO2 fixation to afford a metal-carbonato compound incorporating 1,1-ethenedithiolate ligands. In sharp contrast, reaction with an isobutyl ester-substituted 2-cyanoethylene-1,1-dithiolate forms a trimeric zinc complex [Zn(tmeda){S2CC(CN)(CO2(i)Bu)}]3, 2, which does not contain the metal-bound carbonate. Compound 2 is the first example of a trinuclear zinc complex composed of four-, five-, and six-coordinated Zn atoms. The unsymmetrical ligand orientation around three zinc centers in 2 suggests that the other structural isomer, which would have an idealized C3 axis, may exist. The reaction of the ethyl ester derivative of 2-cyanoethylene-1,1-dithiolate with [Zn(tmeda)Cl2] affords [{Zn(tmeda)Cl}2{S2CC(CN)(CO2Et)}], 3. The ester-functionalized 1,1-dithiolate ligands in compounds 2 and 3 display a bimetallic, triconnective coordination mode, which is rare for these types of ligands. Some probable intermediates generated from the formation of compound 1 have also been proposed.

The reaction of [CpFe(CO)2]2 with NH4Se2P(OR)2 yields a novel reagent Cp(CO)2FeP(Se)(OR)2, which has demonstrated coordination properties at the Se center to form heterometallic clusters as well as reactivity at the Se site toward C-based electrophiles.

The first 2D metal-organic framework utilizing PPh2(CH2)2PPh2 (dppe) units as the linkers and tetranuclear silver clusters, [Ag4(micro3)-Cl){S2P(OR)2}3], as the network nodes in the formation of the honeycomb-shaped layer structure is reported.

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The novel halide-centered Ag(I)8 cubic clusters containing diethyl diselenophosphato ligands are prepared and their solid state structures, a discrete unit or a one-dimensional chain, are dictated by the counter anions.