Manganese carbonyl compounds as hydrosilation catalysts for organoiron acyl complexes

Journal Article · Tue Jan 01 00:00:00 EST 1991 · Organometallics; (United States)

DOI:https://doi.org/10.1021/om00047a017· OSTI ID:6070313

Hanna, P K; Gregg, B T; Cutler, A R ^[1]

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1. Rensselaer Polytechnic Inst., Troy, NY (United States)

Manganese acyl complexes L(CO){sub 4}MnCOR (L = CO, R = CH{sub 3}, Ph; L = PPh{sub 3}, PEt{sub 3}, R = CH{sub 3}) are effective catalysts (2-5%) for hydrosilating FpCOR compounds (R = CH{sub 3}, Ph; Fp = Fe(CO){sub 2}({eta}{sup 5}-C{sub 5}H{sub 5})) with monohydro-, dihydro-, and trihydrosilanes. Fp({alpha}-siloxyalkyl) complexes FpCH(CH{sub 3})OSiR{prime}{sub 3} (SiR{prime}{sub 3} = SiEt{sub 3}, SiMe{sub 2}Ph, SiHPh{sub 2}, SiHEt{sub 2}), (FpCH(CH{sub 3})O){sub 2}SiR{prime}{sub 2} (R{prime} = Et, Ph), FpCH(Ph)OSiHPh{sub 2}, and (FpCH(CH{sub 3})O){sub 3}SiPh are isolated (after column chromatography on silica gel or on polystyrene (size-exclusion) beads) and fully characterized. Substituted manganese acetyl compounds L(CO){sub 4}MnCOCH{sub 3} are extremely active catalysts that quantitatively transform FpCOCH{sub 3} and dihydrosilanes R{prime}{sub 2}SiH{sub 2} (R{prime} = Et, Ph) to Fp({alpha}-siloxyalkyl) complexes FpCH(CH{sub 3})OSiHR{prime}{sub 2}. The manganese acetyl catalysts endure (within NMR spectral detection limits) until all of the organoiron acyl substrate is consumed; only then do they undergo rapid hydrosilation. Other manganese complexes, including (CO){sub 5}MnSiMe{sub 3}, Mn{sub 2}(CO){sub 10}, (CO){sub 5}MnCH{sub 3}, and (CO){sub 5}MnCHPh(OSiHR{prime}{sub 2}), also catalyze the hydrosilation of FpCOCH{sub 3}.

• OSTI ID: 6070313
• Journal Information: Organometallics; (United States), Vol. 10:1, Issue 1; ISSN 0276-7333
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
IRON COMPLEXES
CHEMICAL PREPARATION
MOLECULAR STRUCTURE
MANGANESE COMPLEXES
CATALYTIC EFFECTS
CARBONYLS
LIQUID COLUMN CHROMATOGRAPHY
MANGANESE
NUCLEAR MAGNETIC RESONANCE
ORGANIC SILICON COMPOUNDS
ORGANOMETALLIC COMPOUNDS
PHOSPHINES
CHROMATOGRAPHY
COMPLEXES
ELEMENTS
MAGNETIC RESONANCE
METALS
ORGANIC COMPOUNDS
PHOSPHORUS COMPOUNDS
RESONANCE
SEPARATION PROCESSES
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENTS
400201* - Chemical & Physicochemical Properties