Reactivity of the Y 3+ tuck-over hydride complex, (C 5Me 5) 2Y(μ-H)(μ-CH 2C 5Me 4)Y(C 5Me 5)

Benjamin M. Schmiege, Megan E. Fieser, Joseph W. Ziller, William J. Evans

Research output: Contribution to journalArticlepeer-review

12 Scopus citations

Abstract

The trivalent yttrium tuck-over hydride complex, (C 5Me 5) 2Y(μ-H)(μ-η 15- CH 2C 5Me 4)Y(C 5Me 5), 1, acts as a reductant in reactions in which the (μ-H) - hydride ligand and the bridging Y-C alkyl anion linkage in the (μ-η 1: η 5-CH 2C 5Me 4) 2- ligand combine to form a C-H bond in (C 5Me 5) - and deliver two electrons to a substrate. Complex 1 reacts with PhSSPh, AgOTf (OTf = OSO 2CF 3), and Et 3NHBPh 4 to form [(C 5Me 5) 2Y(μ-SPh)] 2, [(C 5Me 5) 2Y(μ-OTf)] 2, and (C 5Me 5) 2Y(μ-Ph) 2BPh 2, respectively. The reactivity of the Y-H and Y-CH 2C 5Me 4 linkages in 1 was probed via carbodiimide insertion reactions. iPrN=C=N iPr inserts into both Y-H and Y-C bonds to yield (C 5Me 5)[ iPrNC(H)N iPr]Y{μ- η 5-C 5Me 4CH 2[ iPrNCN iPr]}Y(C 5Me 5) 2. Carbodiimide insertion with [(C 5Me 5) 2YH] 2, 2, was also examined for comparison, and (C 5Me 5) 2Y[ iPrNC(H)N iPr- κ 2N,N′] was isolated and structurally characterized. To examine the possibility of selective reactivity of the bridging ligands, μ-H versus μ-CH 2C 5Me 4, trimethylsilylchloride was reacted with 1, and the tuck-over chloride complex, (C 5Me 5) 2Y(μ-Cl)(μ-η 15- CH 2C 5Me 4)Y(C 5Me 5), was isolated.

Original languageEnglish (US)
Pages (from-to)5591-5598
Number of pages8
JournalOrganometallics
Volume31
Issue number15
DOIs
StatePublished - Aug 13 2012

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