Synthesis and Structure of Stable Tri-<i>tert</i>-butylgermyl-Substituted Stannylene and Germylene

Setaka, Wataru; Sakamoto, Kenkichi; Kira, Mitsuo; Power, Philip P.

doi:10.1021/om010591h

Cited by 57 publications

(42 citation statements)

References 22 publications

(16 reference statements)

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“…Each tin is two-coordinate and is bonded to the ipso carbon of the central ring of the terphenyl ligand as well as to the Fe(η 5 -C 5 H 5 )(CO) 2 group through a direct Sn−Fe bond. The Sn−Fe distances (2.5634(5) Å (3), 2.6040(16) Å (4)) are similar to the 2.56 Å predicted from the sum of the covalent radii 25 23 and Ar Pri 6 SnSnPh 2 Ar Pri 6 (108.48(6)°). 34 Reactivity of 1−4 under UV Irradiation.…”

Section: ■ Experimental Sectionsupporting

confidence: 68%

Synthesis, Characterization, and CO Elimination of Ferrio-Substituted Two-Coordinate Germylenes and Stannylenes

et al. 2011

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The reactions of [ArE(Cl)] 2 (E = Ge, Sn; Ar = −C 6 H 3 -2,6-(C 6 H 3 -2,6-i Pr 2 ) 2 (Ar Pri 4 ), −C 6 H 3 -2,6-(C 6 H 2 -2,4,6-i Pr 3 ) 2 (Ar Pri 6 )) with K[(η 5 -C 5 H 5 )Fe(CO) 2 ] afforded the deep green ferriogermylenes ArGeFe(η 5 -C 5 H 5 )(CO) 2 (Ar = Ar Pri 4 (1), Ar Pri 6 (2)) and the ferriostannylenes ArSnFe(η 5 -C 5 H 5 )(CO) 2 (Ar = Ar Pri 4 (3), Ar Pri 6 (4)), respectively. Complexes 1−4 were characterized by NMR, UV−vis, and IR spectroscopy, as well as by X-ray crystallography. The solid-state structures of 1−4 feature two-coordinate Ge or Sn atoms with bent C−E−Fe (E = Ge, Sn) geometries. Although germylenes 1 and 2 remain intact upon heating or UV irradiation, stannylenes 3 and 4 were shown to eliminate one carbonyl group upon exposure to UV light, affording the brown dimeric species {ArSnFe(η 5 -C 5 H 5 )(CO)} 2 (Ar = Ar Pri 4 (5), Ar Pri 6 (6)), respectively.

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Section: ■ Experimental Sectionsupporting

confidence: 68%

Synthesis, Characterization, and CO Elimination of Ferrio-Substituted Two-Coordinate Germylenes and Stannylenes

et al. 2011

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“…The reaction of BbtGeGeBbt (Bbt=2,6‐bis[bis(trimethylsilyl)methyl]‐4‐[tris(trimethylsilyl)methyl]‐phenyl) with 2,3‐dimethyl‐1,3‐butadiene gave a bis(3,4‐dimethylgermacyclopent‐3‐ene) derivative without cleavage of the GeGe bond 17. In contrast, the reactions of butadiene with mononuclear carbene analogues often proceed through [1+4] cycloaddition reactions 12a–c. Hence, the formation of aluminacyclopentene derivatives 4 a and 4 b might result from the :AlL monomer that is generated by the reduction of dialumane 1 with sodium metal (see below).…”

Section: Resultsmentioning

confidence: 99%

Reactivity of Dialumane and “Dialumene” Compounds toward Alkenes

Zhao

Lei

Dong

et al. 2013

Chemistry A European J

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The reactions of dialumane [L(thf)Al-Al(thf)L] (1, L=[{(2,6-iPr2C6H3)NC(Me)}2](2-)) with stilbene and styrene afforded the oxidation/insertion products [L(thf)Al(CH(Ph)-CH(Ph))AlL] (2) and [L(thf)Al(CH(Ph)-CH2)Al(thf)L] (3), respectively. In the presence of Na metal, precursor 1 reacted with butadienes, possibly through the reduced "dialumene" or the "carbene-like" :AlL species, to yield aluminacyclopentenes [LAl(CH2C(Me)=C(Me)CH2)Na]n (4 a) and [Na(dme)3][LAl(CH2C(Me)=CHCH2)] (4 b, dme=dimethoxyethane) as [1+4] cycloaddition products, as well as the [2+4] cycloaddition product 1,6-dialumina-3,8-cyclodecadiene, [{Na(dme)}2][LAl(CH2C(Me)=C(Me)CH2)2AlL] (5). The possible mechanisms of the cycloaddition reactions were studied by using DFT computations.

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“…This result is in contrast to the 29 Si NMR spectroscopic studies (see above), in which the linear and cyclic species could not be differentiated. However, the 119 Sn NMR chemical shifts of organotin compounds cover a range of 5200 ppm with two extremes at d = 2960 ppm for (2,6-Mes 2 C 6 H 3 )SnA C H T U N G T R E N N U N G (tBu 3 Ge) [41] and at d = À2247 ppm for (h 5 -Me 5 4 ]. [42] With such a sensitive nucleus, it is feasible that different linear and cyclic species give different 119 Sn NMR resonances; however, the assignment of all of the measured peaks was not possible.…”

Section: Full Papermentioning

confidence: 99%

Cyclic and Linear Polyferrocenes with Silicon and Tin as Alternating Bridges

Bagh

Breit

Dey

et al. 2012

Chemistry A European J

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The synthesis and characterization of ferrocene-based oligomers that contained two different elements (Si and Sn) as alternating bridges is described for the first time. The salt-metathesis reaction of R(2) Si[(C(5) H(4) )Fe(C(5) H(4) Li)](2) (R=Me, Et) with R'(2) SnCl(2) (R'=Me, nBu, tBu) afforded a mixture of oligomers (6(Me) SnMe(2), 6(Et) SnMe(2), 6(Me) SnnBu(2), 6(Et) SnnBu(2), 6(Me) SntBu(2), and 6(Et) SntBu(2)). These oligomers were characterized by (1) H, (13) C, (29) Si, and (119) Sn NMR spectroscopy and by mass spectrometry. MS (MALDI-TOF) studies of 6(Et) SnMe(2) revealed the presence of linear (l) and cyclic (c) species that contained up to 20 ferrocene moieties. The molecular weights of the polymers were determined by gel-permeation chromatography (GPC) and by dynamic-light scattering (DLS). GPC analysis revealed average molecular weights of 2100-6300 Da with respect to polystyrene as a standard. DLS analysis yielded very similar results. Some compounds, c-(6(Me) SnMe(2) )(1), c-(6(Me) SntBu(2))(2), c-(6(Et) SnMe(2))(1), c-(6(Et) SntBu(2))(2), l-(6(Me) SnnBu(2) )(2), and l-(6(Me) SnnBu(2))(3), which contained up to six ferrocene moieties, were isolated in their pure form either by column chromatography or by crystallization. The Si- and Sn-bridged macrocycles that contained four ferrocene units (c-(6(Me) SntBu(2))(2) and c-(6(Et) SntBu(2))(2)) were structurally characterized by single-crystal X-ray analysis.

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Synthesis and Structure of Stable Tri-tert-butylgermyl-Substituted Stannylene and Germylene

Cited by 57 publications

References 22 publications

Synthesis, Characterization, and CO Elimination of Ferrio-Substituted Two-Coordinate Germylenes and Stannylenes

Synthesis, Characterization, and CO Elimination of Ferrio-Substituted Two-Coordinate Germylenes and Stannylenes

Reactivity of Dialumane and “Dialumene” Compounds toward Alkenes

Cyclic and Linear Polyferrocenes with Silicon and Tin as Alternating Bridges

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