Lewis-Base Adducts of Group 11 Metal(I) Compounds. LXVIII Synthesis and Structural Systematics of Some 1 : 3 Adducts of Silver(I) Compounds with Triphenylstibine, [(Ph3Sb)3AgX], X = Cl, I, SCN, NCS, CN, ONO2

Abstract

The syntheses and room-temperature single-crystal X-ray structural characterization of 1 : 3 adducts formed between silver(I) (pseudo-) halides, AgX, and triphenylstibine, SbPh₃, are described for X = Cl, I, SCN, NCS, CN, NO₃ (1)-(6). The chloride, as its methanol solvate (1a), is isomorphous with the arsine analogue: triclinic, P^-1, a 13·373(4), b 14·48(6), c 14·702(3) Å, α 83·49(3), β 87·76(2), γ 76·45(3)°; Z = 2, conventional R on F being 0·046 for N_o 5514 independent ‘observed’ reflections (I > 3σ(I )). A new form (1b) of the chloride has also been authenticated: monoclinic, P 2₁/c, a 12·832(2), b 54·24(1), c 18·519(8) Å, β 129·68(3)°; Z = 8 (R 0·065 for N_o 5672). No bromide has been obtained; the iodide (2) is described as monoclinic, P 2₁/n, a 19·611(4), b 14·473(6), c 17·74(1) Å, β 98·28(3)°; Z = 4 (R 0·036 for N_o 6769). The thiocyanate crystallizes from acetonitrile or pyridine as an S-bonded form (3) isomorphous with the arsine analogue: monoclinic, P 2₁/n, a 19·143(7), b 14·288(5), c 18·694(6) Å, β 98·81(2)°; Z = 4 (R 0·037 for N_o 4482). From 2-methylpyridine, remarkably, a solvate is obtained in which the thiocyanate is N-bonded (4): triclinic, P^-1, a 27·261(5), b 14·767(3), c 13·319(1) Å, α 91·53(1), β 101·58(1), γ 92·29(2)°; Z = 4 (R 0·045 for N_o 6900). The cyanide is also monoclinic, P 2₁/n, a 19·442(7), b 14·267(3), c 17·741(6) Å, β 97·63(3)°, z = 4; R 0·057 for N_o 2487. The unsolvated 1 : 3 nitrate complex (6a) is monoclinic, P 2₁/n, a 19·602(5), b 14·455(1), c 17·727(2) Å, β 97·19(2)°, Z = 4; R was 0·034 for N_o 6522. The complex is isomorphous with the arsenic and phosphorus analogues, being mononuclear [(Ph₃Sb)₃Ag(O₂NO)]. The ethanol solvate (6b) is triclinic, P^-1, a 13·352(5), b 14·548(9), c 14·701(4) Å, α 81·64(4), β 84·45(3), γ 75·32(4)°, Z = 2; R was 0·058 for N_o 4702. Ag-Sb range between 2·6980(8) and 2·843(3) Å in the precise determinations; Ag-X are 2·481(4) and 2·52(1) Å (the two chlorides), 2·757(1) (I), 2·533(3) (SCN), 2·21(1) (NCS), 2· 09(3) (CN), 2·377(7) Å (unidentate ONO₂)