Synthesis and characterization of the silver maleonitrilediselenolates and silver maleonitriledithiolates [K([2.2.2]-cryptand)]4[Ag4 (Se2C2(CN)2)4], [Na([2.2.2]-cryptand)]4[Ag4 (S2C2(CN)2)4]·0.33MeCN

C. C. McLauchlan, J. A. Ibers*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

21 Scopus citations

Abstract

Reaction of AgBF4, KNH2, K2Se, Se, and [2.2.2]-cryptand in acetonitrile yields [K([2.2.2]-cryptand)]4[Ag4 (Se2C2(CN)2)4] (1). In the unit cell of 1 there are four [K([2.2.2]-cryptand)]+ units and a tetrahedral Ag4 anionic core coordinated in μ1-Se, μ2-Se fashion by each of four mns ligands (mns = maleonitrilediselenolate, [Se2C2(CN)2]2-). Reaction of AgNO3, Na2(mnt) (mnt = maleonitriledithiolate, [S2C2(CN)2]2-), and [2.2.2]-cryptand in acetonitrile yields [Na([2.2.2]-cryptand)]4[Ag4 (mnt)4]·0.33MeCN (2). The Ag4 anion of 2 is analogous to that in 1. Reaction of AgNO3, Na2(mnt), and [NBu4]Br in acetonitrile yields [NBu4]4[Ag4(mnt)4] (3). The anion of 3 also comprises an Ag4 core coordinated by four mnt ligands, but the Ag4 core is diamond-shaped rather than tetrahedral. Reaction of [K([2.2.2]-cryptand)]3[Ag(mns)(Se6)] with KNH2 and [2.2.2]-cryptand in acetonitrile yields [K([2.2.2]-cryptand)]3[Ag(mns)2]·2MeCN (4). The anion of 4 comprises an Ag center coordinated by two mns ligands in a tetrahedral arrangement. Reaction of AgNO3, 2 equiv of Na2(mnt), and [2.2.2]-cryptand in acetonitrile yields [Na([2.2.2]-cryptand)]3[Ag(mnt)2] (5). The anion of 5 is analogous to that of 4. Electronic absorption and infrared spectra of each complex show behavior characteristic of metal-maleonitriledichalcogenates. Crystal data (153 K): 1, P2/n, Z = 2, a = 18.362(2) Å, b = 16.500(1) Å, c = 19.673(2) Å, β = 94.67(1)°, V = 5941(1) Å3; 2, P4̄, Z = 4, a = 27.039(4) Å, c = 15.358(3) Å, V = 11229(3) Å3; 3, P21/c, Z = 6, a = 15.689(3) Å, b = 51.924(11) Å, c = 17.393(4) Å, β = 93.51(1)°, V = 14142(5) Å3; 4, P21/c, Z = 4, a = 13.997(1) Å, b = 21.866(2) Å, c = 28.281(2) Å, β = 97.72(1)°, V = 8578(1) Å3; 5, P2/n, Z = 2, a = 11.547(2) Å, b = 11.766(2) Å, c = 27.774(6) Å, β = 91.85(3)°, V = 3772(1) Å3.

Original languageEnglish (US)
Pages (from-to)1809-1815
Number of pages7
JournalInorganic chemistry
Volume40
Issue number8
DOIs
StatePublished - Apr 9 2001

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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