SYNTHESIS, NMR-STUDY, AND REACTIVITY OF ISOMERIC EARLY-LATE HETEROBIMETALLIC DIHYDRIDES - X-RAY CRYSTAL-STRUCTURE OF PPH(3))HRU(MU-H)(MU-PME(2)C(5)ME(4))(2)(MU-CL)ZRCL

Citation
Vi. Bakhmutov et al., SYNTHESIS, NMR-STUDY, AND REACTIVITY OF ISOMERIC EARLY-LATE HETEROBIMETALLIC DIHYDRIDES - X-RAY CRYSTAL-STRUCTURE OF PPH(3))HRU(MU-H)(MU-PME(2)C(5)ME(4))(2)(MU-CL)ZRCL, Inorganic chemistry, 35(25), 1996, pp. 7316-7324
Citations number
74
Categorie Soggetti
Chemistry Inorganic & Nuclear
Journal title
ISSN journal
00201669
Volume
35
Issue
25
Year of publication
1996
Pages
7316 - 7324
Database
ISI
SICI code
0020-1669(1996)35:25<7316:SNAROI>2.0.ZU;2-A
Abstract
The new isomeric ruthenium/zirconium dihydrides of the formula (PPh(3) )HRuH(mu-PMe(2)Cp)(2)ClZrCl (1, 2) (Cp* = C(5)Me(4)) have been charac terized by elemental analysis and NMR (H-1, P-31 and H-1 relaxation da ta). Complex 1, stabilized by Cl and H bridges, has been isolated from the room temperature reaction between RuH2(H-2)(PPh(3))(3) and (PMe(2 )Cp)(2)ZrCl2. The X-ray crystallographic study of 1 revealed a bimeta llic complex. The six-coordinate Ru atom and the five-coordinate Zr at om are held together by two bifunctional phosphinocyclopentadienyl lig ands and by H and Cl bridges. Crystal data for 1: monoclinic space gro up P2(1)/c, a = 13.901(2) Angstrom, b = 18.205(6) Angstrom, c = 16.633 (3) Angstrom, beta = 92.43(1)degrees, V = 4206 Angstrom(3), Z = 4, d(c alc) = 1.472 g cm(-3), R(F) = 0.056, R(w)(F) = 0.058. Complex 2 with t wo H bridges and terminal Cl ligands at Ru and Zr has been obtained by an irreversible isomerization of 1 in the presence of HNEt(3)BPh(4). This transformation has been proposed to occur through slow protonatio n of one of the phosphorus ligands with the five-coordinate Ru center formed by undergoing rapid pseudorotation. Complexes 1 and 2 do not re act with H-2, N-2, or 3,3-dimethyl-but-1-ene. Treatment of 1 with 1 eq uiv of NaHBEt(3) in C6D6 gives a mixture of new trihydrides (PPh(3))HR u(mu-Cl)(mu-H)(mu-PMe(2)Cp)(2)ZrH (3) and (PPh(3))HRu(mu-H)(2)(mu-PMe (2)Cp)(2)ZrCl (4). Complex 3 transforms to 4 upon standing in solutio n for a period of several days. Under the same conditions, complex 2 l eads smoothly to trihydride 4. Both trihydrides are new and have been characterized by H-1, P-31 NMR, and H-1 NMR relaxation data. Complexes 1 and 4 are fluxional in solution at room temperature. showing hydrid e exchange between the terminal and bridging positions. The variable-t emperature H-1 NMR spectra allowed determinations of the Delta G(doubl e dagger) values of 16.4 (313 K, THF-d(8)) and 13.5 kcal/mol (295 K, t oluene-d(8)) for the exchange in complexes 1 and 4, respectively. Poss ible exchange mechanisms have been discussed. Complex 2 is rigid on th e NMR time scale.