Reaction of an alkyne with dinickel-diphenylsilyl complexes. An emissive disilane formed via the consecutive Si–C and Si–Si bond-making processes

Tanabe, Makoto; Yumoto, Ryouhei; Osakada, Kohtaro

doi:10.1039/c2cc16063c

Cited by 35 publications

(26 citation statements)

References 49 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The molecular structure of 11 (Figure ) resembles those of the group 10 complexes [(L)M(μ-SiHR 2 )M(L)] (M = Ni, Pd, Pt; L = PCy 3 , IPr 2 H 2 ; R = alkyl and aryl). ,− It contains a Co 2 Si 2 diamond core with a Co–Co distance of 2.599(1) Å, a Si–Si distance of 3.78 Å, and nonequivalent Co–Si distances of 2.246(1) and 2.336(1) Å. The Co–Si distances, in addition with the distances of Co1–H and Si1A–H (1.58(3) and 1.66(3) Å, respectively), suggest the 3c-2e bond nature of the Co-(η 2 -H-Si) interactions.…”

Section: Resultssupporting

confidence: 80%

Low-Coordinate NHC-Cobalt(0)-Olefin Complexes: Synthesis, Structure, and Their Reactions with Hydrosilanes

2017

View full text Add to dashboard Cite

The one-pot reaction of CoCl with 1 or 2 equiv of N-heterocyclic carbene (NHC) ligands, vinyltrimethylsilane (vtms), and 2 equiv of reducing reagents (KC or Na(Hg)) proved an effective protocol for the synthesis of three-coordinate NHC-cobalt(0)-olefin complexes, and by which the new low-coordinate cobalt(0) complexes [(NHC)Co(vtms)] (NHC = 1,3-di(2',6'-diethylphenyl)-4,5-(CH)-imidazol-2-ylidene (cyIDep), 6; 1,3-diadamantylimidazol-2-ylidene (IAd), 7) and [(NHC)Co(vtms)] (NHC = 1-(2',4',6'-trimethylphenyl)-3-cyclohexylimidazol-2-ylidene (IMesCy), 8; 1,3-dicyclohexylimidazol-2-ylidene (ICy), 9) were prepared in moderate yields and further characterized by spectroscopic methods. The NHC-cobalt(0)-vtms complexes can serve as low-coordinate NHC-cobalt(0) precursors to react with hydrosilanes. From the reactions of PhSiH with the corresponding NHC-cobalt(0)-vtms complexes, the cobalt silyl complexes [(cyIDep)(H)Co(μ-η:η-HSiPh)(μ-η-HSiPh)Co(H)(cyIDep)] (10), [(NHC)Co(μ-η-SiHPh)Co(NHC)] (NHC = IPr, 13; IAd, 14), and [(IMesCy)Co(H)(SiHPh)] (15) were synthesized. Further reactivity studies established the thermal decomposition of 10 to give [(cyIDep)Co(μ-η-HSiPh)Co(cyIDep)] (11), H, and PhSiH, the reaction of 11 with BuNC (4.5 equiv) to afford [(cyIDep)(BuNC)Co(μ-η-HSiPh)Co(CNBu)] (12) and cyIDep, as well as the conversion of 15 to a silyl-functionalized NHC-cobalt(II) complex 16 upon eliminating H. These cobalt silyl complexes have been characterized by single-crystal X-ray diffraction studies, NMR, absorption, and infrared spectroscopies, as well as elemental analyses. The diversified reaction outcomes demonstrate the rich reaction chemistry of low-coordinate NHC-cobalt(0) complexes.

show abstract

Section: Resultssupporting

confidence: 80%

Low-Coordinate NHC-Cobalt(0)-Olefin Complexes: Synthesis, Structure, and Their Reactions with Hydrosilanes

2017

View full text Add to dashboard Cite

show abstract

“…The products that have been obtained from the reactions of hydrosilanes with transition metal complexes are summarized in Tables (primary silanes), − (secondary silanes), ,− ,, and (tertiary silanes)primarily for products that contain a Si–TM bond. Some researchers study reactions of primary and/or secondary and/or tertiary silanes.…”

Section: Reactions Of Hydrosilanes With Transition Metal Complexesmentioning

confidence: 99%

“… 38 4-45 was also prepared by reaction Cp 2 Fe + B(Ar F ) 4 with (dtbpe)Ni-SiHMes 2 in 85% yd 39 At −60 C in C 7 D 8 , the SiH resonance is observed at 6.25 ppm with 1 J SiH = 167.9 Hz). , 40 4-47 was also prepared from 4-49 and 2 equiv of dmpe 41 29 Si was not observed due to decomposition of the complex during the measurement …”

Section: Reactions Of Hydrosilanes With Transition Metal Complexesmentioning

confidence: 99%

“…This includes the simplest metal compounds, such as MCl 2 , such as reported by Peters and co-workers, and other metal chlorides that also contain replaceable olefins and phosphines (partial listing of examples): (COD)RuCl 2 , [(COE) 2 MCl] 2 (M = Rh, 102 Ir 131 ), [(COD)MCl] 2 (M = Rh, 196 Ir 192 ), and [(COD)PdMeCl] . Other commercial sources contain M(0) coordinated to phosphines and/or olefins, for example: [Ni(COD) 2 ], , Ni(PPh 3 ) 4 , Pd(*PEt 3 ) 4 , and Pt(PPh 3 ) 4 . Selected examples of the use of metal halides in the preparation of complexes that were then used to react with a hydrosilane are shown in eqs and 19 and similarly from a commercial reagent in eq 18 .…”

Section: Reactions Of Hydrosilanes With Transition Metal Complexesmentioning

confidence: 99%

See 1 more Smart Citation

Reactions of Hydrosilanes with Transition Metal Complexes

2016

View full text Add to dashboard Cite

This third review in a series involving reactions of hydrosilanes and transition metal complexes and characterization of the products covers the period 2009 thru 2013. After a brief discussion of other synthetic methods used for the formation of Si-TM complexes, Section 3 provides an extended discussion of the types of ligands and metal complexes used as reactants with hydrosilanes. The increase in use of pincer ligands in forming stable, isolable complexes is featured. Three tables list the complexes reported for primary, secondary, and tertiary silanes. Many reactions leading to SiTM complexes are initiated by loss of a ligand prior to oxidative addition of the hydrosilane or by a metathesis reaction. Structural data are tabulated for the isolated complexes and provide the Si-TM bond ranges for the elements in the "d" block. A major section on nonclassical (σ or agostic) complexes includes two general groupings with Si-H···TM and M-H···Si interactions. A section on solution processes identified by NMR spectroscopy is dominated by hydride exchange examples. A section on bonding outlines a unifying bonding description that has been proposed as well as calculations reported for Si-TM complexes, both real and hypothetical examples.

show abstract

“…In our search for alternative, more efficient catalysts, we identified nickel complexes that were reported previously to activate both C À C [35][36][37][38][39][40][41][42] and Si À H bonds, [43][44][45] and we chose to continue our efforts by employing the well-defined nickel catalyst [NiA C H T U N G T R E N N U N G (PPhMe 2 ) 4 ]. [46] Treatment of 1 with Et 2 SiH 2 and 5 mol % [NiA C H T U N G T R E N N U N G (PPhMe 2 ) 4 ] in toluene at 110 8C resulted in a fast reaction with concomitant release of H 2 .…”

Section: Resultsmentioning

confidence: 99%

Efficient Access to Substituted Silafluorenes by Nickel‐Catalyzed Reactions of Biphenylenes with Et₂SiH₂

Breunig

Gupta

Das

et al. 2014

Chemistry An Asian Journal

View full text Add to dashboard Cite

The reaction of biphenylene (1) with Et2SiH2 in the presence of [Ni(PPhMe2)4] results in the formation of a mixture of 2-diethylhydrosilylbiphenyl [2(Et2HSi)] and 9,9,-diethyl-9-silafluorene (3). Silafluorene 3 was isolated in 37.5% and 2(Et2HSi) in 36.9% yield. The underlying reaction mechanism was elucidated by DFT calculations. 4-Methyl-9,9-diethyl-9-silafluorene (7) was obtained selectively from the [Ni(PPhMe2)4]-catalyzed reaction of Et2SiH2 and 1-methylbiphenylene. By contrast, no selectivity could be found in the Ni-catalyzed reaction between Et2SiH2 and the biphenylene derivative that bears tBu substituents in the 2- and 7-positions. Therefore, two pairs of isomers of tBu-substituted silafluorenes and of the related diethylhydrosilylbiphenyls were formed in this reaction. However, a subsequent dehydrogenation of the diethylhydrosilylbiphenyls with Wilkinson's catalyst yielded a mixture of 2,7-di-tert-butyl-9,9-diethyl-9-silafluorene (8) and 3,6-di-tert-butyl-9,9-diethyl-9-silafluorene (9). Silafluorenes 8 and 9 were separated by column chromatography.

show abstract

Reaction of an alkyne with dinickel-diphenylsilyl complexes. An emissive disilane formed via the consecutive Si–C and Si–Si bond-making processes

Cited by 35 publications

References 49 publications

Low-Coordinate NHC-Cobalt(0)-Olefin Complexes: Synthesis, Structure, and Their Reactions with Hydrosilanes

Low-Coordinate NHC-Cobalt(0)-Olefin Complexes: Synthesis, Structure, and Their Reactions with Hydrosilanes

Reactions of Hydrosilanes with Transition Metal Complexes

Efficient Access to Substituted Silafluorenes by Nickel‐Catalyzed Reactions of Biphenylenes with Et₂SiH₂

Contact Info

Product

Resources

About

Reaction of an alkyne with dinickel-diphenylsilyl complexes. An emissive disilane formed via the consecutive Si–C and Si–Si bond-making processes

Cited by 35 publications

References 49 publications

Low-Coordinate NHC-Cobalt(0)-Olefin Complexes: Synthesis, Structure, and Their Reactions with Hydrosilanes

Low-Coordinate NHC-Cobalt(0)-Olefin Complexes: Synthesis, Structure, and Their Reactions with Hydrosilanes

Reactions of Hydrosilanes with Transition Metal Complexes

Efficient Access to Substituted Silafluorenes by Nickel‐Catalyzed Reactions of Biphenylenes with Et2SiH2

Contact Info

Product

Resources

About

Efficient Access to Substituted Silafluorenes by Nickel‐Catalyzed Reactions of Biphenylenes with Et₂SiH₂