ISSN:
1572-8862
Keywords:
Platinum
;
ruthenium
;
alkynyl-vinylidene tautomerization
;
heteronuclear clusters
Source:
Springer Online Journal Archives 1860-2000
Topics:
Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
,
Physics
Notes:
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.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1007/BF01170717
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