Substitution and fragmentation reactions of Br/sub 2/Os/sub 3/(CO)/sub 12/ with phosphines. Structure of Br/sub 2/Os/sub 3/(CO)/sub 10/(P(OMe)/sub 3/)/sub 2/

Journal Article · Wed Apr 09 00:00:00 EST 1986 · Inorg. Chem.; (United States)

DOI:https://doi.org/10.1021/ic00228a012· OSTI ID:5742768

Chen, Y S; Wang, S L; Jacobson, R A; Angelici, R J

At room temperature the linear complex Br/sub 2/Os/sub 3/(CO)/sub 12/ reacts with PPh/sub 3/ and PPh/sub 2/Me to give the substituted product Br/sub 2/Os/sub 3/(CO)/sub 10/(PR/sub 3/)/sub 2/ (approx. 15%), as well as the mononuclear products Os(CO)/sub 4/PR/sub 3/ (approx. 60%) and Br/sub 2/Os(CO)/sub 2/(PR/sub 3/)/sub 2/ (approx. 15%). The mononuclear products are not formed from Br/sub 2/Os/sub 3/(CO)/sub 10/(PR/sub 3/)/sub 2/ under the conditions of the reaction. The reaction is completely stopped by added CCl/sub 4/ or galvinoxyl, suggesting that the formation of both the trinuclear and mononuclear products are radical processes. From the reaction of Br/sub 2/Os/sub 3/(CO)/sub 12/ with P(OMe)/sub 3/, the trinuclear complex Br/sub 2/Os/sub 3/(CO)/sub 10/(P(OMe)/sub 3/)/sub 2/ is isolated in 53% yield. This complex crystallizes in the centrosymmetric triclinic space group P1 with a = 8.923 (3) A, b = 11.657 (3) A, c = 8.185 (3) A, ..cap alpha.. = 99.48 (3)/sup 0/, ..beta.. = 111.91 (3)/sup 0/, ..gamma.. = 96.28 (3)/sup 0/, and Z = 1.

• Research Organization: Iowa State Univ., Ames
• DOE Contract Number: W-7405-ENG-82
• OSTI ID: 5742768
• Journal Information: Inorg. Chem.; (United States), Vol. 25:8
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
CARBONYLS
CHEMICAL REACTIONS
CRYSTAL STRUCTURE
COMPLEXES
OSMIUM COMPOUNDS
PHOSPHINES
EXPERIMENTAL DATA
DATA
INFORMATION
NUMERICAL DATA
PHOSPHORUS COMPOUNDS
REFRACTORY METAL COMPOUNDS
TRANSITION ELEMENT COMPOUNDS
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