Functionalized bis(pyrazol-1-yl)methanes by organotin halide on the methine carbon atom and their related reactions

Wen, Zhen-Kang; Xie, Yong‐Rong; Zhao, Shu‐Bin; Tan, Runyu; Tang, Liang‐Fu

doi:10.1016/j.jorganchem.2008.01.041

Cited by 14 publications

(5 citation statements)

References 57 publications

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“…As shown in Figure , the organotin group is still connected to the methine carbon and lies in the axial position of the ligand. The fundamental molecular framework is similar to that in ( p -MeC 6 H 4 ) 3 SnCH(3,5-Me 2 Pz) 2 W(CO) 4 …”

Section: Resultsmentioning

confidence: 85%

“…The X-ray crystal structure of complex 9 consists of two crystallographically independent molecules with similar structural parameters. One of them is presented in Figure , which clearly shows that the bridging carbon of bis(pyrazol-1-yl)methide is integrated with the tungsten atom to form two four-membered heterometallacyclyes, as in complexes CH(3,4,5-Me 3 Pz) 2 W(CO) 3 SnPh 3 and CH(3,5- i Pr 2 Pz) 2 W(CO) 3 SnPh 3 …”

Section: Resultsmentioning

confidence: 99%

“…Bis(pyrazol-1-yl)methane, modified by organic functional groups on the bridging carbon atom to form heteroscorpionate ligands, is currently drawing extensive attention, , and its application has also been increasingly exploited in recent years. − Our recent investigations on bis(pyrazol-1-yl)methane indicate that the modification of this ligand with organometallic groups on the methine carbon atom can provide unusual reactivity . For example, the reaction of triarylstannylbis(3,5-dimethylpyrazol-1-yl)methane with W(CO) 5 THF results in the oxidative addition of the Sn−C sp3 bond to the tungsten(0) atom to give the novel four-membered metallacyclic complex, while the analogous reaction of di( tert -butyl)phenylstannylbis(3,5-dimethylpyrazol-1-yl)methane results in the oxidative addition of the Sn−C sp2 bond to the tungsten(0) atom.…”

Section: Introductionmentioning

confidence: 99%

“…For example, the reaction of triarylstannylbis(3,5-dimethylpyrazol-1-yl)methane with W(CO) 5 THF results in the oxidative addition of the Sn−C sp3 bond to the tungsten(0) atom to give the novel four-membered metallacyclic complex, while the analogous reaction of di( tert -butyl)phenylstannylbis(3,5-dimethylpyrazol-1-yl)methane results in the oxidative addition of the Sn−C sp2 bond to the tungsten(0) atom. Interestingly, the similar reaction of trialkylstannylbis(3,5-dimethylpyrazol-1-yl)methane with W(CO) 5 THF gives only heterobimetallic complexes R 3 SnCH(3,5-Me 2 Pz) 2 W(CO) 4 (R = alkyl) …”

Section: Introductionmentioning

confidence: 99%

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Bis(3,5-dimethylpyrazol-1-yl)acyl and Bis(3,5-dimethylpyrazol-1-yl)methide Carbonyl Tungsten Derivatives

et al. 2008

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Supplementary Tables (Tables S1-S17 = 14 Pages) C(1)-W(1)-N(3) 174.0(4) N(2)-C(8)-C(7) 104.3(10) C(28)-C(29)-C(24) 121.3(10) C(3)-W(1)-N(3) 100.5(4) N(2)-C(8)-C(9) 123.9(11) N(2)-C(41)-N(4) 110.8(7) C(2)-W(1)-N(3) 95.1(4) C(7)-C(8)-C(9) 131.7(11) N(2)-C(41)-Sn(1) 110.9(6) C(4)-W(1)-N(1) 107.1(4) N(3)-C(11)-C(12) 111.1(9) N(4)-C(41)-Sn(1) 123.9(6) C(1)-W(1)-N(1) 94.7(4) N(3)-C(11)-C(10) 121.7(9) C(23)-C(18)-C(19) 117.1(9) C(3)-W(1)-N(1) 171.8(4) C(12)-C(11)-C(10) 127.0(10) C(23)-C(18)-Sn(1) 121.9(7) C(2)-W(1)-N(1) 89.1(4) C(13)-C(12)-C(11) 106.1(10) N(1)-N(2)-C(41) 119.4(8) N(3)-W(1)-N(1) 80.3(3) C(12)-C(13)-N(4) 107.5(9) C(11)-N(3)-N(4) 104.3(7) C(6)-N(1)-N(2) 105.5(8) C(12)-C(13)-C(14) 129.3(9) C(8)-N(2)-C(41) 127.8(9) C(6)-N(1)-W(1) 130.4(7) N(4)-C(13)-C(14) 123.1(10) C(15)-C(16)-Sn(1) 109.1(7) N(2)-N(1)-W(1) 122.8(6) C(17)-C(16)-C(15) 111.6(10) C(17)-C(16)-Sn(1) 111.2(7) C(8)-N(2)-N(1) 112.2(9)

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Section: Resultsmentioning

confidence: 85%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Bis(3,5-dimethylpyrazol-1-yl)acyl and Bis(3,5-dimethylpyrazol-1-yl)methide Carbonyl Tungsten Derivatives

et al. 2008

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“…Emphasizing the novelty of the metal complexes described (M ≠ Au), a search in the Cambridge Crystallographic database 52 showed that, while κ 3 E,N 2 -ligands (E = group-14 atom in no specific position within the ligand scaffold) are very well represented for E = Si, 53 very few examples are known for the heavier group-14 elements; in particular, they are only known for E = Sn (tungsten complexes featuring κ 3 N 2 ,Sn organotin-functionalized bis(pyrazol-1-yl)methane ligands). 54 The coordination chemistry of bis(amidinato)stannylene Sn(bqfam) 2 (2b) was not investigated in detail since an initial assessment resulted in discouraging results.…”

Section: 31°mentioning

confidence: 99%

Amidinatotetrylenes Donor Functionalized on Both N Atoms: Structures and Coordination Chemistry

Alonso,

Cabeza,

García-Álvarez

et al. 2024

Inorg. Chem.

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E(hmds)(bqfam) (E = Ge (1a), Sn (1b); hmds = N(SiMe3)2, bqfam = N,N′-bis(quinol-8-yl)formamidinate), which are amidinatotetrylenes equipped with quinol-8-yl fragments on the amidinate N atoms, have been synthesized from the formamidine Hbqfam and Ge(hmds)2 or SnCl(hmds). Both 1a and 1b are fluxional in solution at room temperature, as the E atom oscillates from being attached to the two amidinate N atoms to being chelated by an amidinate N atom and its closest quinolyl N atom (both situations are similarly stable according to density functional theory calculations). The hmds group of 1a and 1b is still reactive and the deprotonation of another equivalent of Hbqfam can be achieved, allowing the formation of the homoleptic derivatives E(bqfam)2 (E = Ge, Sn). The reactions of 1a and 1b with [AuCl(tht)] (tht = tetrahydrothiophene), [PdCl2(MeCN)2], [PtCl2(cod)] (cod = cycloocta-1,5-diene), [Ru3(CO)12] and [Co2(CO)8] have been investigated. The gold(I) complexes [AuCl{κE-E(hmds)(bqfam)}] (E = Ge, Sn) have a monodentate κE-tetrylene ligand and display fluxional behavior in solution the same as that of 1a and 1b. However, the palladium(II) and platinum(II) complexes [MCl{κ3 E,N,N′ -ECl(hmds)(bqfam)}] (M = Pd, Pt; E = Ge, Sn) contain a κ3 E,N,N′-chloridotetryl ligand that arises from the insertion of the tetrylene E atom into an M–Cl bond and the coordination of an amidinate N atom and its closest quinolyl N atom to the metal center. Finally, the binuclear ruthenium(0) and cobalt(0) complexes [Ru2{μE-κ3 E,N,N′ -E(hmds)(bqfam)}(CO)6] and [Co2{μE-κ3 E,N,N′ -E(hmds)(bqfam)}(μ-CO)(CO)4] (E = Ge, Sn) have a related κ3 E,N,N′ -tetrylene ligand that bridges two metal atoms through the E atom. For the κ3 E,N,N′-metal complexes, the quinolyl fragment not attached to the metal is pendant in all the germanium compounds but, for the tin derivatives, is attached to (in the Pd and Pt complexes) or may interact with (in the Ru2 and Co2 complexes) the tin atom.

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Synthesis and Reactivity of Group 6 Metal Carbonyl Complexes with Bis(pyrazol‐1‐yl)methanes Modified by the Vinyltin Groups

et al. 2009

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Diphenyl(vinyl)stannylbis(3,5-dimethylpyrazol-1-yl)methane and diphenyl(vinyl)stannylbis(3,4,5-trimethylpyrazol-1-yl)methane have been synthesized by the reaction of bis(3,5-dimethylpyrazol-1-yl)methyl or bis(3,4,5trimethylpyrazol-1-yl)methyllithium with diphenyl(vinyl)tin iodide. Treatment of these bis(pyrazol-1-yl)methanes modified by the vinyltin groups with M(CO) 5 THF (M＝Mo and W) in refluxing THF resulted in new heterobimetallic complexes R 3 SnCHPz 2 M(CO) 3 (R 3 Sn represents trivinyltin or diphenyl(vinyl)tin, and Pz represents substituted pyrazol-1-yl), in which a vinyl group bonds to the molybdenum or tungsten atom in η 2 -fashion to lead to bis(pyrazol-1-yl)methanes acting as a tridentate κ 3 -(π,N,N) ligand. Reaction of (CH 2 ＝ CH) 3 SnCH(3,5-Me 2 Pz) 2 W(CO) 3 and Ph 2 (CH 2 ＝CH)SnCH(3,5-Me 2 Pz) 2 W(CO) 3 with I 2 has been investigated. The former gave a complex CH 2 (3,5-Me 2 Pz) 2 W(CO) 4 , while the latter yielded a four-membered heterometallocyclic complex CH(3,5-Me 2 Pz) 2 W(CO) 3 I with the loss of the organotin group. Treatment of this four-membered heterometallocyclic complex with PhSNa led to the iodide anion replaced by the thiophenolate anion to give a complex CH(3,5-Me 2 Pz) 2 W(CO) 3 SPh.

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Functionalized bis(pyrazol-1-yl)methanes by organotin halide on the methine carbon atom and their related reactions

Cited by 14 publications

References 57 publications

Bis(3,5-dimethylpyrazol-1-yl)acyl and Bis(3,5-dimethylpyrazol-1-yl)methide Carbonyl Tungsten Derivatives

Bis(3,5-dimethylpyrazol-1-yl)acyl and Bis(3,5-dimethylpyrazol-1-yl)methide Carbonyl Tungsten Derivatives

Amidinatotetrylenes Donor Functionalized on Both N Atoms: Structures and Coordination Chemistry

Synthesis and Reactivity of Group 6 Metal Carbonyl Complexes with Bis(pyrazol‐1‐yl)methanes Modified by the Vinyltin Groups

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