Core conformational rearrangement accompanying two-center, bimetallic redox reactions. Chemical and structural properties of the pyrazolyl-bridged rhodium dimers Rh(. eta. sup 5 -C sub 5 Me sub 5 )Cl(. mu. -pz) sub 2 and Rh(. eta. sup 5 -C sub 5 H sub 5 )(. mu. -pz) sub 2

Journal Article · Thu Feb 01 00:00:00 EST 1990 · Organometallics; (USA)

DOI:https://doi.org/10.1021/om00116a038· OSTI ID:6950803

Balley, J A; Grundy, S L; Stobart, S R ^[1]

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1. Univ. of Victoria, British Columbia (Canada)

Reaction between (Rh({eta}{sup 5}-C{sub 5}Me{sub 5})Cl({mu}-pz)){sub 2} (5), which exhibits a chair conformation for the core pyrazolyl-bridged bimetallic unit in the crystal with Rh{sub 2} separation 4.059 (2) {angstrom}, and AgBf{sub 4} affords (Rh{sub 2}({eta}{sup 5}-C{sub 5}Me{sub 5}){sub 2}({mu}-pz){sub 2}({mu}-Cl))BF{sub 4} (6), in which the cation core exists in a boat conformation with Rh centers 3.588 (2) {angstrom} apart; reduction (Zn/Cu) of 5 yields a purple product (7) tentatively identified as (Rh({eta}{sup 5}-C{sub 5}Me{sub 5})({mu}-pz)){sub 2}, the bright purple, reactive {eta}{sup 5}-C{sub 5}H{sub 5} analogue 9 of which has been synthesized from (Rh({eta}{sup 5}-C{sub 5}H{sub 5})Cl({mu}-pz)){sub 2} (8) and shown by using single-crystal X-ray diffraction to possess a deeply folded (boat) geometry in which Rh-Rh = 2.657 (3) {angstrom}.

• OSTI ID: 6950803
• Journal Information: Organometallics; (USA), Vol. 9:2; ISSN 0276-7333
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
36 MATERIALS SCIENCE
REDOX REACTIONS
RHODIUM COMPLEXES
CHEMICAL PROPERTIES
PHYSICAL PROPERTIES
CALCULATION METHODS
CONFORMATIONAL CHANGES
DATA ANALYSIS
DIMERS
EXPERIMENTAL DATA
LIGANDS
MEASURING INSTRUMENTS
MEASURING METHODS
ORGANOMETALLIC COMPOUNDS
CHEMICAL REACTIONS
COMPLEXES
DATA
INFORMATION
NUMERICAL DATA
ORGANIC COMPOUNDS
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties
360104 - Metals & Alloys- Physical Properties