AI Article Synopsis
- - The reaction of 1,4-diisocyanobenzene or 4-isocyanobenzonitrile with trans-W(N(2))(2)(DPPE)(2) yields cis-WL(2)(DPPE)(2), resulting in two distinct complexes that crystallize in the triclinic space group P&onemacr; with detailed measurements of crystal dimensions.
- - Both complexes exhibit a distorted octahedral geometry around the tungsten center, with the isocyanide ligands arranged in a cis configuration and displaying significant bending along the CNC axis, indicating strong interaction with the tungsten metal.
- - The presence of electron-rich tungsten leads to noticeable back-donation and shifts in C-N stretching frequencies,
Article Abstract
Reaction of 1,4-diisocyanobenzene or 4-isocyanobenzonitrile with trans-W(N(2))(2)(DPPE)(2) (DPPE = 1,2-bis(diphenylphosphino)ethane) produced cis-WL(2)(DPPE)(2), where L = 1,4-diisocyanobenzene or 4-isocyanobenzonitrile. cis-(CNC(6)H(4)NC)(2)W(DPPE)(2) crystallizes in the triclinic space group P&onemacr;, with a = 12.848(3) Å, b = 13.596(3) Å, c = 19.072(3) Å, alpha = 78.99(2) degrees, beta = 70.66(2) degrees, gamma = 65.26(2) degrees, V = 2849.8(11) Å(3), and Z = 2. cis-(NCC(6)H(4)NC)(2)W(DPPE)(2) crystallizes in the triclinic space group P&onemacr;, with a = 12.712(3) Å, b = 13.700(3) Å, c = 19.109(3) Å, alpha = 77.91(2) degrees, beta = 70.63(2) degrees, gamma = 64.76(2) degrees, V = 2830.7(13) Å(3), and Z = 2. Both compounds possess a distorted octahedral geometry about the metal center, with the two isocyanide ligands cis to one another. The isocyanide ligands are substantially bent along the CNC axis of the isocyanide group coordinated to tungsten. For the complex containing the symmetric ligand, CNC(6)H(4)NC, the mean CNC angle for the coordinated end of the isocyanide is 139.1(11) degrees, the average W-C bond length is 1.86(1) Å, and the C&tbd1;N bond lengths have a mean value of 1.30(2) Å. These data indicate substantial back-donation from an electron-saturated tungsten atom. This is supported spectroscopically, with substantial shifts to lower wavenumbers for the C-N stretching frequencies of the coordinated isocyanide groups. Similar trends are observed in cis-(NCC(6)H(4)NC)(2)W(DPPE)(2). Both compounds contain electron-rich metals surrounded by large ligands which apparently protect the metals from atmospheric oxidation. The isocyanide ligands in both complexes contain a second coordinating group pointing away from the metal into the environment surrounding the molecules, providing the potential for polymetallic complexes containing metals in a variety of oxidation states.
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