Conversion of an Acetylide−Silylene Complex to an Alkenylcarbyne Complex by Consecutive Ketone Addition and Base-Induced Silanone Elimination

Sakaba, Hiroyuki; Yabe-Yoshida, Mako; Oike, Hiroyuki; Kabuto, Chizuko

doi:10.1021/om1005879

Cited by 11 publications

(11 citation statements)

References 24 publications

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“…123 10 Hydride was located from Fourier difference synthesis and positionally refined isotropically. 153 11 Other Derivatives: Cr: 2.1603(7); 50 18 2.4562(16); 18 2.471(av); 17 2.4990(8); 19 2.5086(11); 19 2.5125(7); 255 2.5257(12); 256 2.5474(16) (av of 2); 160 2.573(4); 52 2.5991(13); 154 2.608; 252 2.6110(13); 158 2.615(2); 158 2.620(8); 18 2.625(2); 257 2.6399(14); 258 2.6512(7); 254 2.6778 (10). 160 12 Hydrogens were found in the difference Fourier map and refined isotropically.…”

Section: Solid State Structuresmentioning

confidence: 90%

“…120 A more unusual tungsten silylene complex was reported by Sakaba and co-workers from the reaction of Cp*(OC) 2 W-(NCMe)Me and HPh 2 SiCC-SiMe 3 . 160 In this case the silylene ligand interacted with both the W and the acetylide fragment as shown in eq 56. The reactions of this unique silylene and the closely related analog, HPh 2 SiCC-CMe 3 , will be described later in the section that addresses reactions of complexes.…”

Section: Formation Of Silylene Complexes From Si(iv) Precursors and R...mentioning

confidence: 96%

“…A more unusual tungsten silylene complex was reported by Sakaba and co-workers from the reaction of Cp*(OC) 2 W(NCMe)Me and HPh 2 SiCC-SiMe 3 . In this case the silylene ligand interacted with both the W and the acetylide fragment as shown in eq .…”

Section: Reactions Of Hydrosilanes With Transition Metal Complexesmentioning

confidence: 99%

“… 11 Other Derivatives: Cr : 2.1603(7); 2.1618(9); 2.2515(7); 2.2847(6); 2.326(av); 2.329(av); 2.3398(4); 2.3458(7); 2.515(7); Mo: 2.2241(7); 2.287(1) (dble); 2.300(1) (dble); 2.3430(6); 2.3474(6); 2.471(av); 2.4550(14); 2.4562(16); 2.480(av); 2.480(2); 2.4883(8); 2.5125(7); 2.5135(9); 2.515(2); 2.5172(8); 2.519(4); 2.5221(9); 2.5231(19); 2.546(2); 2.5536(13); 2.554(5); 2.5552(17); 2.584(3); 2.608; 2.6178(6); 2.624(3); 2.624; 2.632; 2.634(3); 2.6491(3); 2.654; 2.6659(7); 2.6675(17); 2.9647(8); 247 3.2204(9); 3.4394(10); (last 3 are considered nonbonding). W: 2.376(dble); 2.3760(9); 2.386; 2.4202(14) (dble); 2.4562(16); 2.471(av); 2.4990(8); 2.5086(11); 2.5125(7); 2.5257(12); 2.5474(16) (av of 2); 2.573(4); 2.5991(13); 2.608; 2.6110(13); 2.615(2); 2.620(8); 2.625(2); 2.6399(14); 2.6512(7); 2.6778(10) 12 Hydrogens were found in the difference Fourier map and refined isotropically …”

Section: Solid State Structuresunclassified

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Reactions of Hydrosilanes with Transition Metal Complexes

2016

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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.

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Section: Solid State Structuresmentioning

confidence: 90%

Section: Formation Of Silylene Complexes From Si(iv) Precursors and R...mentioning

confidence: 96%

Section: Reactions Of Hydrosilanes With Transition Metal Complexesmentioning

confidence: 99%

Section: Solid State Structuresunclassified

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Reactions of Hydrosilanes with Transition Metal Complexes

2016

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“…In contrast, studies of the germanium analogues, the germylene complexes L n MGeR 2 , are still relatively limited, especially their reactivity toward organic substrates. We recently synthesized the novel acetylide–silylene complexes Cp*(CO) 2 W(SiPh 2 )(CCR), whose unique bonding nature, dual charge transfer interactions between the silylene and acetylide ligands, has been revealed by a theoretical study . Their interesting reactivity has also been demonstrated; for instance, the reaction of Cp*(CO) 2 W(SiPh 2 )(CCSiMe 3 ) ( 1 ) with acetone resulted in acetone insertion reaction to give the cyclic vinylidene complex Cp*(CO) 2 WCC(SiMe 3 )CMe 2 OSiPh 2 ( 2 ), which reacted with 4-(dimethylamino)pyridine (DMAP) to give the alkenylcarbyne complex Cp*(CO) 2 WCC(CMe 2 )(SiMe 3 ) ( 3 ) and cyclic diphenylsiloxanes ( n = 3, 4) via DMAP-induced diphenylsilanone elimination (Scheme )…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Structure, and Reactivity of Tungsten Acetylide–Germylene Complexes

et al. 2013

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The novel acetylide–germylene complexes Cp*(CO)2W(GePh2)(CCR) (7a, R = SiMe3; 7b, R = CMe3) were synthesized by the reactions of Cp*(CO)2W(NCMe)Me with Ph2HGeCCR (R = SiMe3, CMe3). X-ray crystal analysis of 7a revealed significantly increased germylene–tungsten and decreased germylene–acetylide interactions in comparison to the corresponding interactions in the previously reported acetylide–silylene complex Cp*(CO)2W(SiPh2)(CCSiMe3) (1). Complexes 7a,b reacted with acetone to give the six-membered cyclic vinylidene complexes Cp*(CO)2 WCC(R)CMe2OGePh2 (8a, R = SiMe3; 8b, R = CMe3) by acetone insertion reaction, similar to the case of 1 affording Cp*(CO)2 WCC(SiMe3)CMe2OSiPh2 (2). In the presence of 4-(dimethylamino)pyridine (DMAP), complexes 8a,b gave trans- and cis-DMAP-stabilized germylene acetylide complexes Cp*(CO)2W(GePh2·DMAP)(CCR) ( trans - and cis -9a, R = SiMe3; trans - and cis -9b, R = CMe3) and acetone, showing a reactivity different from that of the silicon analogue 2. Complexes cis- 9a,b were isolated as crystals from the reaction of 7a,b with DMAP and formed mixtures with trans -9a,b in solutions, respectively. A mixture of cis- and trans-9a reacted with acetone to form an equilibrium mixture with 8a and DMAP. The reactivity of 7a,b toward Me3COH was also investigated to reveal the formation of the vinylidene complexes Cp*(CO)2W{GePh2(OCMe3)}CCHR (10a, R = SiMe3; 10b, R = CMe3); 10a is equilibrated with 7a and Me3COH, whereas 10b is further converted to the carbyne complex Cp*(CO)2WCCH(CMe3){GePh2(OCMe3)} (11).

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One‐Pot Synthesis of High‐Strained Metal Vinylidene and Metal Carbyne

Huang

Yan

Zheng

et al. 2022

Chemistry A European J

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A novel one-pot reaction producing a metal vinylidene structure in a five-membered ring by cyclization of a multiyne has been achieved. The ring strain and the high stability of the cyclic metal vinylidene complexes have been analyzed experimentally and computationally. The metal vinylidene unit in a fused-ring complex is unreactive to both nucleophiles and electrophiles. It reacts however at the nearby carbonyl group achieving the unprecedented conversion of metal tributing factors for the aromaticity-driven process has been studied by DFT calculations.

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Conversion of an Acetylide−Silylene Complex to an Alkenylcarbyne Complex by Consecutive Ketone Addition and Base-Induced Silanone Elimination

Cited by 11 publications

References 24 publications

Reactions of Hydrosilanes with Transition Metal Complexes

Reactions of Hydrosilanes with Transition Metal Complexes

Synthesis, Structure, and Reactivity of Tungsten Acetylide–Germylene Complexes

One‐Pot Synthesis of High‐Strained Metal Vinylidene and Metal Carbyne

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