Soft scorpionate coordination at alkali metals

Reported here are the single‐crystal X‐ray structure analyses of bis‐μ‐methanol‐κ4O:O‐bis{[hydrotris(3‐phenyl‐2‐sulfanylidene‐2,3‐dihydro‐1H‐1,3‐imidazol‐1‐yl)borato‐κ3H,S,S′](methanol‐κO)sodium(I)}, [Na2(C27H22BN6S3)2(CH4O)4] (NaTmPh), bis‐μ‐methanol‐κ4O:O‐bis{[hydrotris(3‐isopropyl‐2‐sulfanylidene‐2,3‐dihydro‐1H‐1,3‐imidazol‐1‐yl)borato‐κ3H,S,S′](methanol‐κO)sodium(I)}–diethyl ether–methanol (1/0.3333/0.0833), [Na2(C18H28BN6S3)2(CH4O)4]·0.3333C4H10O·0.0833CH3OH (NaTmiPr), 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)] ([NaTmMe]n). NaTmiPr and NaTmPh have similar dimeric molecular structures with κ3H,S,S′‐bonding, but they differ in that NaTmPh is crystallographically centrosymmetric (Z′ = 0.5) while NaTmiPr contains one crystallographically centrosymmetric dimer and one dimer positioned on a general position (Z′ = 1.5). [NaTmMe]n is a one‐dimensional coordination polymer that extends along the a direction and which contains a hitherto unseen side‐on η2‐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.