title: Soft scorpionate coordination at alkali metals.
abstract: Reported here are the single-crystal X-ray structure analyses of bis-μ-methanol-κ(4)O:O-bis{[hydrotris(3-phenyl-2-sulfanylidene-2,3-dihydro-1H-1,3-imidazol-1-yl)borato-κ(3)H,S,S'](methanol-κO)sodium(I)}, [Na2(C27H22BN6S3)2(CH4O)4] (NaTm(Ph)), bis-μ-methanol-κ(4)O:O-bis{[hydrotris(3-isopropyl-2-sulfanylidene-2,3-dihydro-1H-1,3-imidazol-1-yl)borato-κ(3)H,S,S'](methanol-κO)sodium(I)}-diethyl ether-methanol (1/0.3333/0.0833), [Na2(C18H28BN6S3)2(CH4O)4]·0.3333C4H10O·0.0833CH3OH (NaTm(iPr)), and a novel anhydrous form of sodium hydrotris(methylthioimidazolyl)borate, poly[[μ-hydrotris(3-methyl-2-sulfanylidene-2,3-dihydro-1H-1,3-imidazol-1-yl)borato]sodium(I)], [Na(C12H16BN6S3)] ([NaTm(Me)]n). NaTm(iPr) and NaTm(Ph) have similar dimeric molecular structures with κ(3)H,S,S'-bonding, but they differ in that NaTm(Ph) is crystallographically centrosymmetric (Z' = 0.5) while NaTm(iPr) contains one crystallographically centrosymmetric dimer and one dimer positioned on a general position (Z' = 1.5). [NaTm(Me)]n is a one-dimensional coordination polymer that extends along the a direction and which contains a hitherto unseen side-on η(2)-C=S-to-Na bond type. An overview of the structural preferences of alkali metal soft scorpionate complexes is presented. This analysis suggests that these thione-based ligands will continue to be a rich source of interesting alkali metal motifs worthy of isolation and characterization.
authors.affiliation: WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, 295 Cathedral Street, Glasgow G1 1XL, Scotland.
authors.forename: Rajeev
authors.initials: R
authors.lastname: Rajesekharan-Nair
authors.affiliation: Department of Chemistry and Biochemistry, Chepkoilel University College, Moi University, PO Box 1125, Eldoret, Kenya.
authors.forename: Samuel T
authors.initials: ST
authors.lastname: Lutta
authors.affiliation: WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, 295 Cathedral Street, Glasgow G1 1XL, Scotland.
authors.forename: Alan R
authors.initials: AR
authors.lastname: Kennedy
authors.affiliation: WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, 295 Cathedral Street, Glasgow G1 1XL, Scotland.
authors.forename: John
authors.initials: J
authors.lastname: Reglinski
authors.affiliation: WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, 295 Cathedral Street, Glasgow G1 1XL, Scotland.
authors.forename: Mark D
authors.initials: MD
authors.lastname: Spicer
keywords: DFT analysis; alkali metals; crystal structure; scorpionates