Isolation of the anions [M(CO)5(SH)]and [M2(CO)10(µ-SH)](M = Cr, Mo, and W) as salts of the sodium (18-crown-6-ether) cation. X-Ray analysis of the sodium carbonyl linked ‘polymeric’ structures of the tungsten species

Abstract
Ultraviolet irradiation has provided a convenient synthetic route to the anions [M(CO)5(SH)] and [M2(CO)10(µ-SH)](M = Cr, Mo, and W) which have been isolated as their sodium (18-crown-6-ether) salts. X-Ray analysis of [Na(18-crown-6)][W(CO)5(SH)](1) and of [Na(18-crown-6)][W2(CO)10(µ-SH)](2) have shown them to be chain-polymeric in nature with sodium–carbonyl linkages between alternating cations and anions. The Na–O-(carbonyl) distances are in the range 2.41–2.47 Å. In addition to the Na–O distances, compound (1) also shows a weaker Na–S interaction of 3.01 Å. Crystals of (1) are orthorhombic, space group Pna21 with a= 16.484(3), b= 7.622(2), c= 19.220(3)Å, and Z= 4. Crystals of (2) are triclinic, space group P, with a= 15.014(3), b= 11.874(2), c= 9.636(2)Å, α= 102.28(2), β= 96.29(2), γ= 100.63(2)°, and Z= 2. Data were collected on a four-circle diffractometer using Mo-Kα radiation from a graphite monochromator. Blocked full-matrix refinement converged to R 0.044 for (1) and 0.031 for (2).

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