Abstract
The first order rate constants for the tautomerization of the hydrio(alkynyl) clusters Ru3Pt(μ-H){μ4-ν2-C ≡ C1Bu}(CO)9(L2);1a: L2 = dppe,1b; L2 = dppet,1c; L2 = dppp and1d; L2 =S,S-dppb to the corresponding vinylidene clusters Ru3Pt{μ4-ν2-C = C(H)tBu}(CO)9(L2)2 have been measured, and they follow the orser1d <1a <1b ∼1c. The reactions involving1a and1d exhibit an inverse kinetic deuterium isotope effect. The structures of1b, 2b, 2c, and2d were determined by X-ray crystallography, and are compared with those of1a and2a which have been previously reported. Crystal data for1b, space groupPbca,a = 13.338(4) Å,b = 17.771(6) Å,c = 36.092(8) Å,Z = 8,R(R w) = 0.059(0.058) for 2342 absorption corrected, observed data; for2b, space group P21/n,a = 10.566(2) Å,b = 20.234(5) Å,c = 20.270(3) Å,β = 96.11(1)°,Z = 4,R(R w) = 0.043(0.053) for 5865 absorption corrected, observed data; for2c, space group P21/n,a = 14.211(5) Å,b = 19.534(2) Å,c = 15.870(2) Å,β = 100.81(2)°,Z = 4,R(R w) = 0.055(0.031) for 6566 absorption corrected, observed data: for2d, space group P212121,a = 12.309(4) Å,b = 19.047(6) Å,c = 19.206(4) Å,Z = 4,R(R w) = 0.055(0.053) fpr 2151 absorption corrected, observed data. The fluxional behavior of1d and1e (which consists of two interconverting isomers) has been examined by variable temperature13C NMR spectroscopy and by31P EXSY.
Similar content being viewed by others
References
P. Ewing and L. J. Farrugia (1989).Organometallics 8, 1246.
A. J. Dent, L. J. Farrugia, A. G. Orpen, and S. E. Stratford (1992).J. Chem. Soc., Chem. Commun. 1456.
L. J. Farrugia, N. McDonald, and R. D. Peacock (1991).J. Chem. Soc., Commun. 163.
E. Rosenberg, E. V. Anslyn, C. Barner-Thorson, S. Aime, D. Osella, R. Gobetto, and L. Milone (1984).Organometallics 3, 1790.
L. J. Farrugia (1989).Organometallics 8, 2410.
J. W. Moore and R. G. Pearson,Kinetics and Mechanism (Wiley, New York, 1981).
N. Walker and D. Stuart (1983).Acta Crystallogr., Sect. A: Found. Crystallogr. A39, 158.
C. J. Gilmore (1984).J. Appl. Chem. 17, 42.
A. G. Orpen (1980).J. Chem. Soc., Dalton Trans. 2509.
D. Rodgers (1981).Acta Crystallogr., Sect. A: Found. Crystallogr. A37, 734.
International Tables for X-Ray Crystallogr, Vol. 4 (Kynoch: Birmingahm, 1974).
P. Mallinson and K. W. Muir (1985).J. Appl. Cryst. 18, 51.
E. W. Abel, T. P. J. Coston, K. G. Orrell, V. Sik, and D. Stephenson (1986).J. Magn. Reson. 70, 34.
L. J. Farrugia and S. E. Rae (1992).Organometallics 11, 196.
E. Rosenberg (1989).Polyhedron 8, 383.
L. G. Farrugia (1990).Adv. Organomet. Chem. 31, 301.
L. J. Farrugia (1992).J. Cluster Sci. 3, 361.
A forward rate constantk 1 of 1 × 10−3 min−1 at 302 K implies a barrier ΔG: of ∼ 101 kJ mol−1 fpr the tautomerization of1 →2.
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Farrugia, L.J., McDonald, N. & Peacock, R.D. Further studies on the taumerization of the hydrido (alkynyl) cluster Ru3Pt(μ-H) {μ4-ν2-C ≡ C1Bu} (CO)9(L2) to the vinylidene cluster Ru3Pt{μ4-ν2-C ≡ C(H)tBu} (CO)9(L2): X-ray structures of Ru3Pt(μ-H){μ4-ν2-C = C(H)tBu} (CO)9(L2); L2 = dppet, dppp, andS,S-dppb. J Clust Sci 5, 341–361 (1994). https://doi.org/10.1007/BF01170717
Received:
Issue Date:
DOI: https://doi.org/10.1007/BF01170717