Chemistry of organosilicon compounds. 287. Synthesis and x-ray structure of the first dicoordinate dialkylstannylene that is monomeric in the solid state

Kira, Mitsuo; Yauchibara, Rika; Hirano, R.; Kabuto, Chizuko; Sakurai, Hideki

doi:10.1021/ja00020a064

Cited by 149 publications

(140 citation statements)

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“…For compound A, one single resonance at À85 ppm was reported, which might result from the observed fluxional behavior without defined coordination modes in solution. [4] Consistent with a higher coordination number of four and therefore an increase in 119 Sn nuclear shielding, compound 1 closes a gap in the chemical shifts of organotin(II) compounds, which range from > 2000 ppm for double coordination ([Sn(C{SiMe 3 } 2 CH 2 ) 2 ]: 2323 ppm) [9] to À2000 ppm for two-fold h 5 coordination ([Sn(h 5 -C 5 H 5 ) 2 ]: À2171.1 ppm). [10] Apart from the characteristic terphenyl signals, 1 shows a doublet at 2.78 ppm and a quintet at 5.39 ppm in its 1 H NMR spectrum.…”

Section: Sn{mentioning

confidence: 79%

η³‐Allyl Coordination at Tin(II)—Reactivity towards Alkynes and Benzonitrile

et al. 2015

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We herein report the synthesis and characterization of a terphenyl-substituted Sn(II) allyl compound featuring an η(3) coordination mode in solution and in the solid state. Two examples for the interesting reactivity of the allyl Sn(II) molecule are presented: Reactions with terminal alkynes result in the formation of tricyclic compounds by CC bond formation and the dimerization of two Sn moieties whereas the reaction with benzonitrile leads to a sixteen-membered ring system through CH activation.

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Section: Sn{mentioning

confidence: 79%

η³‐Allyl Coordination at Tin(II)—Reactivity towards Alkynes and Benzonitrile

et al. 2015

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“…[31] Structurally confirmed dialkylstannylenes are also rare, of which the cyclic compound SnC(SiMe 3 ) 2 [CH 2 ] 2 C a (SiMe 3 ) 2 (SnϪC a ) is mentioned as an example. [68] The existence of the SnϪSn double bond in solution was demonstrated not only by variable-temperature 119 Sn-NMR spectroscopy, [58,61] but also by trapping reactions with the heavier chalcogens to give, for example, the new ring systems of the telluradistannirane 64, [59] or the unusual 1,2-dithiadistannetane 65. [60] However, compound 63 cannot be The only reaction of 66 to proceed without isomerization is that with carbon disulfide.…”

Section: Stannylenes Distannenesmentioning

confidence: 99%

Some Silicon, Germanium, Tin, and Lead Analogues of Carbenes, Alkenes, and Dienes

Weidenbruch¹

1999

Eur. J. Inorg. Chem.

203

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The isolation and characterization of thermally stable diaminocarbenes and diaminosilylenes has reawakened interest in the low‐coordinated compounds of group‐14 elements. The existence of these species is presumably due to interactions between the free electron pairs on the nitrogen atoms and the carbene carbon atom or the silicon atom. The present review is mainly concerned with the heavier analogues R2Ge:, R2Sn:, and R2Pb:, systems without intramolecular donor stabilization that owe their existence principally to steric shielding by the voluminous alkyl or aryl groups R. Dimerizations of these electron‐sextet molecules give rise to the double‐bond systems of the digermenes, distannenes, and diplumbenes; the latter species have for a long time been considered as being incapable of existence. The properties of these molecules are compared with the results of quantum chemical calculations. A separate section is devoted to the isomers of Si4R6, which include novel tetrasilacyclobutenes and the diene analogues, the tetrasilabuta‐1,3‐dienes.

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“…3 Since stable dialkylgermylene 2 4 and dialkylstannylene 3 5 with the same helmet ligand had been synthesized prior to silylene 1, a systematic and straightforward discussion of the element dependence of the intrinsic properties of the group-14 element divalent compounds has been made possible by the synthesis of 1. 6 Historically, the first convincing evidence for the generation of dimethylsilylene as a representative of dialkylsilylenes was obtained by the high-temperature thermolysis of the corresponding 7-silanorbornadiene derivative in 1964 (Eq.…”

Section: Introductionmentioning

confidence: 99%

A Helmeted Dialkylsilylene

Kira¹,

Iwamoto²,

Ishida³

2007

Bulletin of the Chemical Society of Japan

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102

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Structural characteristics, spectroscopic properties, and unique reactions of a helmeted dialkylsilylene, 2,2,5,5-tetrakis(trimethylsilyl)silacyclopentane-1,1-diyl, that was synthesized as the first isolable dialkylsilylene and its application to the synthesis of novel silicon unsaturated compounds are surveyed. The silylene was found to be the least electronically perturbed among known stable silylenes by 29 Si NMR and UV-vis spectroscopies. The silylene reacts not only with well-known trapping reagents for transient silylenes, such as alcohols, triethylsilane, and 2,3-dimethylbutadiene, but also with less reactive haloalkanes and halosilanes to give the corresponding adducts. One-electron reduction of the silylene using alkali metals affords the corresponding radical anion as a relatively persistent species at low temperatures in solution. Irradiation of the silylene using visible light generates a singlet excited state with a lifetime of 80.5 ns, which reacts with various aromatic compounds and alkenes to give the corresponding silepins and siliranes in a highly regio-and stereoselective manner. The silylene is utilized for the synthesis of unique silicon unsaturated compounds, such as Si=X doubly bonded compounds (X ¼ S, Se, Te, C=NR, etc.), a trisilaallene, a 1,3-disilagermaallene, and silylene transition-metal complexes.

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Chemistry of organosilicon compounds. 287. Synthesis and x-ray structure of the first dicoordinate dialkylstannylene that is monomeric in the solid state

Cited by 149 publications

References 1 publication

η³‐Allyl Coordination at Tin(II)—Reactivity towards Alkynes and Benzonitrile

η³‐Allyl Coordination at Tin(II)—Reactivity towards Alkynes and Benzonitrile

Some Silicon, Germanium, Tin, and Lead Analogues of Carbenes, Alkenes, and Dienes

A Helmeted Dialkylsilylene

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Chemistry of organosilicon compounds. 287. Synthesis and x-ray structure of the first dicoordinate dialkylstannylene that is monomeric in the solid state

Cited by 149 publications

References 1 publication

η3‐Allyl Coordination at Tin(II)—Reactivity towards Alkynes and Benzonitrile

η3‐Allyl Coordination at Tin(II)—Reactivity towards Alkynes and Benzonitrile

Some Silicon, Germanium, Tin, and Lead Analogues of Carbenes, Alkenes, and Dienes

A Helmeted Dialkylsilylene

Contact Info

Product

Resources

About

η³‐Allyl Coordination at Tin(II)—Reactivity towards Alkynes and Benzonitrile

η³‐Allyl Coordination at Tin(II)—Reactivity towards Alkynes and Benzonitrile