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Avis MW, Elsevier CJ, Veldman N, et al. Monodentate sigma-N and Bidentate sigma-N,sigma-N' Coordination of 1,1-Bis((N-p-tolylimino)diphenylphosphoranyl)ethane, CHCH(3)(PPh(2)=NC(6)H(4)-4-CH(3))(2), to Platinum(II). Inorg Chem. 1996;35(6):1518-1528doi: 10.1021/ic950748w.
Avis, M. W., Elsevier, C. J., Veldman, N., Kooijman, H., & Spek, A. L. (1996). Monodentate sigma-N and Bidentate sigma-N,sigma-N' Coordination of 1,1-Bis((N-p-tolylimino)diphenylphosphoranyl)ethane, CHCH(3)(PPh(2)=NC(6)H(4)-4-CH(3))(2), to Platinum(II). Inorganic chemistry, 35(6), 1518-1528. https://doi.org/10.1021/ic950748w
Avis, Mandy W., et al. "Monodentate sigma-N and Bidentate sigma-N,sigma-N' Coordination of 1,1-Bis((N-p-tolylimino)diphenylphosphoranyl)ethane, CHCH(3)(PPh(2)=NC(6)H(4)-4-CH(3))(2), to Platinum(II)." Inorganic chemistry vol. 35,6 (1996): 1518-1528. doi: https://doi.org/10.1021/ic950748w
Avis MW, Elsevier CJ, Veldman N, Kooijman H, Spek AL. Monodentate sigma-N and Bidentate sigma-N,sigma-N' Coordination of 1,1-Bis((N-p-tolylimino)diphenylphosphoranyl)ethane, CHCH(3)(PPh(2)=NC(6)H(4)-4-CH(3))(2), to Platinum(II). Inorg Chem. 1996 Mar 13;35(6):1518-1528. doi: 10.1021/ic950748w. PMID: 11666367.
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Inorg Chem. 1996 Mar 13;35(6):1518-1528. doi: 10.1021/ic950748w.

Monodentate sigma-N and Bidentate sigma-N,sigma-N' Coordination of 1,1-Bis((N-p-tolylimino)diphenylphosphoranyl)ethane, CHCH(3)(PPh(2)=NC(6)H(4)-4-CH(3))(2), to Platinum(II).

Inorganic chemistry

Mandy W. Avis, Cornelis J. Elsevier, Nora Veldman, Huub Kooijman, Anthony L. Spek

Affiliations

  1. Van't Hoff Research Institute, Anorganisch Chemisch Laboratorium, Universiteit van Amsterdam, Nieuwe Achtergracht 166, 1018 WV Amsterdam, The Netherlands, and Bijvoet Center for Biomolecular Research, Vakgroep Kristal- en Structuurchemie, Universiteit Utrecht, Padualaan 8, 3584 CH Utrecht, The Netherlands.

PMID: 11666367 DOI: 10.1021/ic950748w

Abstract

The new ligand, 1,1-bis((N-p-tolylimino)diphenylphosphoranyl)ethane (1,1-BIPE), 1, has been synthesized by means of a Staudinger reaction of 1,1-bis(diphenylphosphino)ethane (1,1-dppe) with 2 equiv of p-tolylazide. Bridge-splitting reactions of Pt(2)Cl(4)(PR(3))(2) with 1 readily afforded sigma-N monodentate complexes, [PtCl(2)(PR(3)){1,1-BIPE-sigmaN}] (2a, PR(3) = PEt(3); 2b, PR(3) = PMe(2)Ph). Conversion of 2 into the six-membered platinacycle [PtCl(PR(3)){1,1-BIPE-sigmaN,sigmaN'}](+)[X](-) (3) (X = Cl, PtCl(3)(PR(3)), BF(4)) took place after prolonged stirring, its reaction rate being strongly dependent on the type of phosphine (>5 days for 2ain the presence of NaBF(4), 1 h for 2b) and the metal-to-ligand ratio. The compounds 1, 2, and 3 have been fully characterized by (1)H, (31)P{(1)H}, and (13)C{(1)H} NMR and IR spectroscopy, elemental analysis, or FAB mass spectroscopy. The molecular structures of CHCH(3)(PPh(2)=NC(6)H(4)-4-CH(3))(2) (1) and [PtCl(PMe(2)Ph){(N(pTol)=PPh(2))(2)CHCH(3)}](+)[Cl](-) (3b) have been determined by X-ray crystallography. Crystal data for 1: space group P2(1)/c with a = 8.9591(5) Å, b = 19.1961(12) Å, c = 21.9740(9) Å, beta = 105.069(4) degrees, V = 3649.1(3) Å(3), and Z = 4. The structure refinement converged to R = 0.080 and R(w) = 0.109. Crystal data for 3b: monoclinic, space group P2(1)/c with a = 12.4021(7) Å, b = 16.9705(11) Å, c = 23.760(2) Å, beta = 109.544(5) degrees, V = 4712.7(5) Å(3), and Z = 4. The structure refinement converged to R1 = 0.057, wR2 = 0.122. Variable temperature NMR spectroscopy has revealed that complexes 3 exclusively adopt a twisted boat conformation with the methyl group in equatorial position at low temperature, in agreement with the solid state structure of 3b as determined by X-ray crystallography. Boat-to-boat inversion is assumed to take place at temperatures above 293 K. Furthermore, for 3, hindered rotation of one of the p-tolyl substituents on nitrogen has been established at low temperatures.

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