Silver(I)-dithiolate chemistry: Syntheses and characterizations of three new Ag1 cluster anions containingi-MNT [i-MNT= S2CC(CN) in2 su2− ] ligands-[Ag4(i-MNT)4]4−, [Ag8(i-MNT)6(PPh3)4]4−, and [Ag9(i-MNT)6(PPh3)6]3−

Abstract

The reaction of AgNO3 with [(“Bu4N2i-MNT)]3 in CH3CN produces a new silver cluster anion [Ag4(i-MNT)4]4− ,3, a species having a tetrahedral arrangement of silver atoms bridged by fouri-MNT ligands which has been isolated and characterized by X-ray crystallography as [Bu4N]2[(PPh3)2]2 [Ag4(i-MNT)4],4. The reaction of two or three equivalents of Ag(PPh3)2NO3 with [BzEt3N]6[Ag6(i-MNT)6] in CH3CN produces two new clusters, [BzEt3N]4[Ag8(i-MNT)6(PPh3)4],6, and [BzEt3N]3[Ag4(i-MNT)6(PPh3)6], 7, having the common structural feature of an octahedral Ag6S12 core. The octanuclear Ag8 cluster also can be synthesized from the reaction of 4 and PPh3 in CH2Ck2 and compound 5 has been structurally characterized as [Bu4N]2[(PPh3)2N]2[Ag8(i-MNT)6(PPh3)4]. The31P{1H} NMR spectrum of 6 in CD3CN at −43° shows two sets of two doublets. The corresponding chemical shift and coupling constant of each species is 9.32 ppm (354, 408.8 Hz) and 9.45 ppm (346.7, 401.7 Hz), respectively. Pertinent crystallographic data are as follows: Compound 4 crystallizes in the orthorhombic space group Cc2a, witha=18.668(3)A,b=36.793(4) A,c=17.836(3)A, Z=4, andV= 12250(3)A3. Compound 5 crystallizes in the triclinic space group P1, witha=16.506(3)A,b=17.280(3)A,c=19.144(4) A,x=98.485(14)°, β= 105.44(2)°.y=94.63(2),Z= 1, andV = 5164(2)A3. Compound6 crystallizes in the monoclinic space group C2/m, witha= 25.341(9)A,b= 25.289(9)A,c= 15.076(7)A, β= 107.19(5)°,Z=2, and V=9230(6)A3. Compound7 crystallizes in the monoclinic space group C2/c, witha=25.872(6)A,b=21.288(4) A,c=35,928(5), β=100.98(1)°,Z-4, andV=19426(6)A3.