Department of Chemistry, University of British Columbia, Vancouver, British Columbia, Canada V6T 1Z1.
Dalton Trans. 2013 Mar 28;42(12):4291-8. doi: 10.1039/c3dt32909g.
The known green, five-coordinate, square-pyramidal trans-RuCl(2)(P-N)(PPh(3)) complex reversibly binds water, MeOH and EtOH in the vacant coordination site in the solid state and in CH(2)Cl(2) solution to give pink adducts (P-N = o-diphenylphosphino-N,N'-dimethylaniline). The adducts are well characterized, including X-ray analysis of the aqua complex, trans-RuCl(2)(P-N)(PPh(3))(H(2)O), which crystallizes in two different benzene-solvated forms. Comparison of the structural data with those determined previously for the binding of H(2)S, thiols, and H(2), which form cis-RuX(2)(P-N)(PPh(3))L products (X = Cl, Br; L = a S-ligand or H(2)) reveals the trans-influence trend P > H(2)S ~ thiols > H(2) > Cl ~ Br > H(2)O. Thermodynamic data for the binding of water were estimated in solution by UV-Vis spectroscopy, and ΔH(o) data for the aqua and alcohol adducts in the solid state were obtained by differential scanning calorimetry. Inclusion of published data for the S-ligand adducts reveals the thermal stability trend of the solid complexes as MeSH > MeOH > H(2)S > H(2)O > EtSH > EtOH.
已知的绿色、五配位、平面四方反式 RuCl(2)(P-N)(PPh(3)) 配合物在固态和 CH(2)Cl(2)溶液中通过 vacant coordination site 可逆地结合水、MeOH 和 EtOH，生成粉红色加合物（P-N = o-二苯膦基-N,N'-二甲苯胺）。这些加合物得到了很好的表征，包括对水合配合物 trans-RuCl(2)(P-N)(PPh(3))(H(2)O)的 X 射线分析，该配合物在两种不同的苯溶剂化形式中结晶。将结构数据与先前确定的 H(2)S、硫醇和 H(2)的结合数据进行比较，这些配合物形成 cis-RuX(2)(P-N)(PPh(3))L 产物（X = Cl，Br；L = a S-配体或 H(2))，揭示了 trans-影响趋势 P > H(2)S ~ 硫醇 > H(2) > Cl ~ Br > H(2)O。通过紫外可见光谱在溶液中估计了水结合的热力学数据，并通过差示扫描量热法获得了固态水和醇加合物的 ΔH(o)数据。包含已发表的 S-配体加合物数据揭示了固态配合物的热稳定性趋势，MeSH > MeOH > H(2)S > H(2)O > EtSH > EtOH。
