Steric Control of Aggregation in Neutral Silver(I) Thiolates, [AgSR]n. Crystal and Molecular Structures of [AgSCH(SiMe3)2]8, a Discrete Molecular Biscycle of Weakly Interacting [AgSCH(SiMe3)2]4 Units, and of [AgSC(SiphMe2)3]3 and [AgSC(SiMe3)3]4, Discrete Molecular Monocycles Containing Linearly Coordinated Silver(I) and Doubly Bridging Mercapto Sulfur Donors from Novel Sterically Hindered Thiolate Ligands. A Comparison with the Nonmolecular Structure of [Ag4{SCH2(SiMe3)}3]n(OMe)n1

Kaluo Tang, Mohammad Aslam, Eric Block, Terrence Nicholson, Jon Zubieta

Research output: Contribution to journalArticle

101 Scopus citations

Abstract

By the use of a novel series of sterically hindered thiolate ligands, (RR′R″Si)nCH3–n the colorless silver–thiolate complexes [AgSC(SiMe2Ph)3]3 (5a) and [AgSC(SiMe3)3]4 (4a) and the yellow species [AgSCH(SiMe3)2]8 (3a) and [Ag4{SCH2-(SiMe3)}3(OCH3)]n (2a) have been synthesized and structurally characterized. The structure of 5a consists of a discrete nonplanar six-membered cycle of alternating silver and sulfur atoms, Ag3S3, exhibiting no secondary interactions between trinuclear units. In contrast, the structure of 4a consists of a planar eight-membered cycle, Ag4S4, and exhibits unstrained digonal Ag–S coordination, unperturbed by secondary Ag…S interactions. The results suggest that a degree of control of aggregation may be introduced by employing ligands possessing sufficient steric bulk. Furthermore, the reduction of ligand steric hindrance in -SCH(SiMe3)2 has profound structural consequences as illustrated by the structure of 3a, which consists of two weakly interacting [AgSCH(SiMe3)2]4 cycles, facing each other and connected by secondary Ag…S interactions, producing a T-shaped geometry about the Ag centers. Further reduction in the steric bulk of the ligand results in the polymeric structure of 2a. The complex three-dimensional polymer may be described in terms of kinked chains of fused octanuclear Ag4S4 cyclic links cross-linked through bridging Ag4S4 monocycles. Crystal data: for 5a, triclinic P1 α = 11.236 (2) Å, b = 16.445 (3) Å, c = 25.686 (4) Å, α = 92.79 (1)°, ß = 97.52 (1)°, γ = 108.77 (1)°, V = 4434.2 (9) Å3, Dcalcd = 1.34 g cm–3 for Z = 2, R = 0.061 for 9537 reflections; for 4a, orthorhombic Pbca, a = 17.478 (3) Å, b = 28.314 (4) Å, c = 29.706 (4) Å, V = 14700.6 (12) Å3, Dcalcd = 1.28 g cm–3 for Z = 8, R = 0.069 for 2759 reflections; for 3a, monoclinic C2/c, α = 18.339 (4) Å, b = 24.623 (4) Å, c = 24.473 (4) Å, ß = 96.74 (1)°, V = 10974.6 (11) Å3, Dcalcd = 1.45 g cm–3 for Z = 4, R = 0.063 for 3919 reflections; for 2b, monoclinic C2/c, α = 17.023 (3) Å, b = 29.470 (5) Å, c = 23.372 (4) Å, ß = 104.21 (1)°, V = 11366.2 (14) Å3, Dcalcd = 1.92 g cm–3 for Z = 16, R = 0.069 for 1366 reflections.

Original languageEnglish (US)
Pages (from-to)1488-1497
Number of pages10
JournalInorganic Chemistry
Volume26
Issue number10
DOIs
StatePublished - Jan 1 1987
Externally publishedYes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Fingerprint Dive into the research topics of 'Steric Control of Aggregation in Neutral Silver(I) Thiolates, [AgSR]<sub>n</sub>. Crystal and Molecular Structures of [AgSCH(SiMe<sub>3</sub>)<sub>2</sub>]<sub>8</sub>, a Discrete Molecular Biscycle of Weakly Interacting [AgSCH(SiMe<sub>3</sub>)<sub>2</sub>]<sub>4</sub> Units, and of [AgSC(SiphMe<sub>2</sub>)<sub>3</sub>]<sub>3</sub> and [AgSC(SiMe<sub>3</sub>)<sub>3</sub>]<sub>4</sub>, Discrete Molecular Monocycles Containing Linearly Coordinated Silver(I) and Doubly Bridging Mercapto Sulfur Donors from Novel Sterically Hindered Thiolate Ligands. A Comparison with the Nonmolecular Structure of [Ag<sub>4</sub>{SCH<sub>2</sub>(SiMe<sub>3</sub>)}<sub>3</sub>]<sub>n</sub>(OMe)<sub>n</sub><sup>1</sup>'. Together they form a unique fingerprint.

  • Cite this