Cobalt(0) and Iron(0) Isocyanides as Catalysts for Alkene Hydrosilylation with Hydrosiloxanes

Atsushi Sanagawa, Hideo Nagashima

Research output: Contribution to journalArticle

7 Citations (Scopus)

Abstract

Iron and cobalt isocyanides, Fe(CNR)5 (1) and Co2(CNR)8 (2), where R = t-butyl (tBu), adamantyl (Ad), and mesityl (Mes), were prepared by reduction of FeBr2 or CoI2 in the presence of CNR by C8K or silica-Na. These complexes were subjected to catalytic hydrosilylation of alkenes with hydrosiloxanes, and the results are compared with those obtained by previously reported Fe(OPiv)2/CNAd or Co(OPiv)2/CNAd catalyst systems. Hydrosilylation of allylic ethers with 1,1,1,3,3-pentamethyldisiloxane (PMDS) catalyzed by 1 and the reaction of several alkenes with PMDS or 1,1,1,3,5,5,5-heptamethyltrisiloxane (MD′M) catalyzed by 2 exhibited greater catalytic activity than that observed for the Fe(OPiv)2 or Co(OPiv)2/CNR catalyst system. Complexes 1 and 2 were effective for catalytic chemical modification of silicone fluids containing Si-H groups and for two-component silicone curing. In all cases, selectivity of the reaction in terms of formation of the desired product by hydrosilylation and of byproducts due to dehydrogenative silylation did not differ between the metal isocyanide complexes and the corresponding M(OPiv)2/CNR catalyst system. Catalytically active species generated from 1, 2, and the M(OPiv)2/CNR catalyst system were also investigated.

Original languageEnglish
Pages (from-to)2859-2871
Number of pages13
JournalOrganometallics
Volume37
Issue number17
DOIs
Publication statusPublished - Sep 10 2018

Fingerprint

Hydrosilylation
Cyanides
Alkenes
Cobalt
alkenes
cobalt
Iron
iron
catalysts
Catalysts
silicones
Silicones
Ethers
Chemical modification
Metal complexes
curing
Silicon Dioxide
Byproducts
Curing
catalytic activity

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

Cite this

Cobalt(0) and Iron(0) Isocyanides as Catalysts for Alkene Hydrosilylation with Hydrosiloxanes. / Sanagawa, Atsushi; Nagashima, Hideo.

In: Organometallics, Vol. 37, No. 17, 10.09.2018, p. 2859-2871.

Research output: Contribution to journalArticle

@article{5bc4c454aee04da99cff4bf19922e375,
title = "Cobalt(0) and Iron(0) Isocyanides as Catalysts for Alkene Hydrosilylation with Hydrosiloxanes",
abstract = "Iron and cobalt isocyanides, Fe(CNR)5 (1) and Co2(CNR)8 (2), where R = t-butyl (tBu), adamantyl (Ad), and mesityl (Mes), were prepared by reduction of FeBr2 or CoI2 in the presence of CNR by C8K or silica-Na. These complexes were subjected to catalytic hydrosilylation of alkenes with hydrosiloxanes, and the results are compared with those obtained by previously reported Fe(OPiv)2/CNAd or Co(OPiv)2/CNAd catalyst systems. Hydrosilylation of allylic ethers with 1,1,1,3,3-pentamethyldisiloxane (PMDS) catalyzed by 1 and the reaction of several alkenes with PMDS or 1,1,1,3,5,5,5-heptamethyltrisiloxane (MD′M) catalyzed by 2 exhibited greater catalytic activity than that observed for the Fe(OPiv)2 or Co(OPiv)2/CNR catalyst system. Complexes 1 and 2 were effective for catalytic chemical modification of silicone fluids containing Si-H groups and for two-component silicone curing. In all cases, selectivity of the reaction in terms of formation of the desired product by hydrosilylation and of byproducts due to dehydrogenative silylation did not differ between the metal isocyanide complexes and the corresponding M(OPiv)2/CNR catalyst system. Catalytically active species generated from 1, 2, and the M(OPiv)2/CNR catalyst system were also investigated.",
author = "Atsushi Sanagawa and Hideo Nagashima",
year = "2018",
month = "9",
day = "10",
doi = "10.1021/acs.organomet.8b00389",
language = "English",
volume = "37",
pages = "2859--2871",
journal = "Organometallics",
issn = "0276-7333",
publisher = "American Chemical Society",
number = "17",

}

TY - JOUR

T1 - Cobalt(0) and Iron(0) Isocyanides as Catalysts for Alkene Hydrosilylation with Hydrosiloxanes

AU - Sanagawa, Atsushi

AU - Nagashima, Hideo

PY - 2018/9/10

Y1 - 2018/9/10

N2 - Iron and cobalt isocyanides, Fe(CNR)5 (1) and Co2(CNR)8 (2), where R = t-butyl (tBu), adamantyl (Ad), and mesityl (Mes), were prepared by reduction of FeBr2 or CoI2 in the presence of CNR by C8K or silica-Na. These complexes were subjected to catalytic hydrosilylation of alkenes with hydrosiloxanes, and the results are compared with those obtained by previously reported Fe(OPiv)2/CNAd or Co(OPiv)2/CNAd catalyst systems. Hydrosilylation of allylic ethers with 1,1,1,3,3-pentamethyldisiloxane (PMDS) catalyzed by 1 and the reaction of several alkenes with PMDS or 1,1,1,3,5,5,5-heptamethyltrisiloxane (MD′M) catalyzed by 2 exhibited greater catalytic activity than that observed for the Fe(OPiv)2 or Co(OPiv)2/CNR catalyst system. Complexes 1 and 2 were effective for catalytic chemical modification of silicone fluids containing Si-H groups and for two-component silicone curing. In all cases, selectivity of the reaction in terms of formation of the desired product by hydrosilylation and of byproducts due to dehydrogenative silylation did not differ between the metal isocyanide complexes and the corresponding M(OPiv)2/CNR catalyst system. Catalytically active species generated from 1, 2, and the M(OPiv)2/CNR catalyst system were also investigated.

AB - Iron and cobalt isocyanides, Fe(CNR)5 (1) and Co2(CNR)8 (2), where R = t-butyl (tBu), adamantyl (Ad), and mesityl (Mes), were prepared by reduction of FeBr2 or CoI2 in the presence of CNR by C8K or silica-Na. These complexes were subjected to catalytic hydrosilylation of alkenes with hydrosiloxanes, and the results are compared with those obtained by previously reported Fe(OPiv)2/CNAd or Co(OPiv)2/CNAd catalyst systems. Hydrosilylation of allylic ethers with 1,1,1,3,3-pentamethyldisiloxane (PMDS) catalyzed by 1 and the reaction of several alkenes with PMDS or 1,1,1,3,5,5,5-heptamethyltrisiloxane (MD′M) catalyzed by 2 exhibited greater catalytic activity than that observed for the Fe(OPiv)2 or Co(OPiv)2/CNR catalyst system. Complexes 1 and 2 were effective for catalytic chemical modification of silicone fluids containing Si-H groups and for two-component silicone curing. In all cases, selectivity of the reaction in terms of formation of the desired product by hydrosilylation and of byproducts due to dehydrogenative silylation did not differ between the metal isocyanide complexes and the corresponding M(OPiv)2/CNR catalyst system. Catalytically active species generated from 1, 2, and the M(OPiv)2/CNR catalyst system were also investigated.

UR - http://www.scopus.com/inward/record.url?scp=85052953309&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85052953309&partnerID=8YFLogxK

U2 - 10.1021/acs.organomet.8b00389

DO - 10.1021/acs.organomet.8b00389

M3 - Article

AN - SCOPUS:85052953309

VL - 37

SP - 2859

EP - 2871

JO - Organometallics

JF - Organometallics

SN - 0276-7333

IS - 17

ER -