Monocyclopentadienylzirconium and -hafnium alkyls: Synthesis, hydrogen-transfer reactions, and catalytic features in the reactivity with. alpha. -olefins. X-ray structure of CpZr(. eta. sup 4 -butadiene)(dmpe)Cl (dmpe = 1,2,bis(dimethylphosphino)ethane)

Journal Article · Wed Feb 28 23:00:00 EST 1990 · Organometallics; (USA)

DOI:https://doi.org/10.1021/om00117a007· OSTI ID:6438736

Wielstra, Y; Gambarotta, S ^[1]; Spek, A L ^[2]

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1. Rijksuniversiteit Groningen (Netherlands)
2. Rijksuniversiteit Utrecht (Netherlands)

The dissociation of one of the two equatorial dmpe (dmpe = 1,2-bis(dimethylphosphino)ethane) of CpM(dmpe){sub 2}X (X = Cl (1), Me (2); M = Zr (a), Hf (b)), allows the preparation of the new class of butadiene derivatives CpM({eta}{sup 4}-butadiene)(dmpe)X (X = Cl (4a,b), Me (5a)), via mild-condition ligand-replacement reaction. The structure of 4 was demonstrated by X-ray diffraction analysis. Crystal data are as follows: monoclinic, P2{sub 1}/n, a = 8.230 (1), b = 15.896 (1), c = 16.571 (1), {beta} = 95.43 (1), Z = 4, R = 0.043, R{sub w} = 0.044 for 2,634 observed reflections. The symmetrical {eta}{sup 4} bonding mode of the butadiene moiety suggests that the low-valent character of zirconium is preserved on these compounds. Complex 4 is the starting material for the preparation of a series of linear alkyl and hydride derivatives CpM({eta}{sup 4}-butadiene)(dmpe)X (X = H (6a,b), Et (7), n-Pr (10), n-Bu (11)) via a simple substitution reaction.

• OSTI ID: 6438736
• Journal Information: Organometallics; (USA), Journal Name: Organometallics; (USA) Vol. 9:3; ISSN 0276-7333; ISSN ORGND
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
COMPLEXES
CRYSTAL STRUCTURE
DATA
DATA ANALYSIS
EXPERIMENTAL DATA
HAFNIUM COMPLEXES
HYDROGEN TRANSFER
INFORMATION
MEASURING INSTRUMENTS
MEASURING METHODS
NUMERICAL DATA
REACTIVITY
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
ZIRCONIUM COMPLEXES