Molecular structure of 1,1-dimethylhydrazine

Litvinov, O. A.; Ermolaeva, L. V.; Зверев, В. В.; Naumov, V. A.

doi:10.1007/bf00761309

Cited by 3 publications

(2 citation statements)

References 10 publications

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“…The TiN α and N α −N β distances for 13 and 14 are identical within error, whereas those for 15 are shorter and longer, respectively. A similar trend in N α −N β distance was found for the calixarene-supported compounds 5 , and group 4 N β -dialkyl-substituted hydrazides generally have longer N α −N β distances and pyramidal N β atoms. , The N α −N β single bond in free Me 2 NNH 2 (1.436(2) Å, pyramidal N Me 2 ) is likewise longer than that in Ph 2 NNH 2 (1.418(2) Å, planar N Ph 2 ), apparently due to N β hybridization effects. , …”

Section: Resultssupporting

confidence: 58%

Reactions of Cyclopentadienyl−Amidinate Titanium Hydrazides with CO₂, CS₂, and Isocyanates: Ti═N_α Cycloaddition, Cycloaddition−Insertion, and Cycloaddition−NNR₂ Group Transfer Reactions

et al. 2011

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We report a comprehensive combined experimental and DFT investigation of the synthesis, molecular and electronic structures, and reactivity of terminal hydrazido complexes with CO 2 , CS 2 , isocyanates, and isothiocyanates. Reaction of Cp*Ti{MeC(N i Pr) 2 }(N t Bu) with hydrazines R 1 R 2 NNH 2 gave the structurally characterized series of hydrazides Cp*Ti{MeC(N i Pr) 2 }(NNR 1 R 2 ) (R 1 = Ph, R 2 = Ph (13), Me (14); R 1 = R 2 = Me (15)). The energetics of this imide/hydrazine exchange reaction, as well as the electronic and molecular structures of 13-15, have been evaluated by DFT and compared with those of their methyl and phenyl imido counterparts. Reaction of 13-15 with CO 2 or CS 2 gave TidN R cycloaddition products of the type Cp*Ti{MeC(N i Pr) 2 }{N(NR 2 )C(E)E} (R = Ph, Me; E = O, S) and, in the case of CO 2 , cycloaddition-insertion products Cp*Ti{MeC-(N i Pr) 2 }{OC(O)N(NR 2 )C(O)O}, in which 2 equivs of CO 2 had effectively inserted into TidN R . Reaction of 13 with isocyanates and isothiocyanates also gave stable cycloaddition products. Cp*Ti{MeC(N i Pr) 2 }{N(NPh 2 )C(NTol)O} reacted further with CO 2 to give a mixed cycloaddition-insertion product. The t BuNCO moiety in Cp*Ti{MeC(N i Pr) 2 }{N(NPh 2 )C(N t Bu)O} could be displaced by CO 2 or TolNCO. In contrast, the reactions of 15 are dominated by cycloaddition-elimination reactions. Reaction with t BuNCO or Ar 0 NCO (2 equivs) gave t BuNCNNMe 2 or the heterocycle 1,2,4-N(Me) 2 NC(NAr 0 )N(Ar 0 )C(O), respectively, along with [Cp*Ti{MeC-(N i Pr) 2 }(μ-O)] 2 . With TolNCO (2 equivs), Cp*Ti{MeC(N i Pr) 2 }{OC(NNMe 2 )N(Tol)C(NTol)O} was formed via a series of cycloaddition-elimination and cycloaddition-insertion steps. The energetics and mechanisms of the cycloaddition, cycloaddition-insertion, and cycloaddition-extrusion processes of various model imido and hydrazido complexes have been investigated using DFT. In the latter (metathesis) reactions, the reaction outcomes depend on a delicate balance of the relative affinities of NR or NNR 2 for the metal center or the organic fragment (CO, CS, or RNC).

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Section: Resultssupporting

confidence: 58%

Reactions of Cyclopentadienyl−Amidinate Titanium Hydrazides with CO₂, CS₂, and Isocyanates: Ti═N_α Cycloaddition, Cycloaddition−Insertion, and Cycloaddition−NNR₂ Group Transfer Reactions

et al. 2011

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“…1.40−1.45 Å) bonds. ,, Note that these N−N single bond averages vary significantly depending on the formal hybridization of the nitrogen (N(sp 2 )−N(sp 2 ) < N(sp 2 )−N(sp 3 ) < N(sp 3 )−N(sp 3 )). The experimental N α −N β distance in Me 2 NNH 2 (both nitrogens formally sp 3 hybridized) is 1.436(2) Å, and is clearly much longer than the N α −N β distance in 3 .…”

Section: Resultsmentioning

confidence: 83%

Synthesis, Structures and Reactivity of Group 4 Hydrazido Complexes Supported by Calix[4]arene Ligands

et al. 2008

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Reaction of TiCl(2)(Me(2)Calix) with 2 equiv of LiNHNRR' afforded the corresponding terminal hydrazido(2-) complexes Ti(NNRR')(Me(2)Calix) (R = Ph, R' = Ph (1) or Me; R = R' = Me (3)) which were all structurally characterized. The X-ray structure of Ph(2)NNH(2) is reported for comparison. Compound 1 was also prepared from Na(2)[Me(2)Calix] and Ti(NNPh(2))Cl(2)(py)(3). Reaction of ZrCl(2)(Me(2)Calix) with 2 equiv of LiNHNR(2) afforded only the bis(hydrazido(1-)) complexes Zr(NHNR(2))(2)(Me(2)Calix) (R = Ph or Me). Treatment of Ti(NNMe(2))(Me(2)Calix) (3) with MeI gave the zwitterionic hydrazidium species Ti(NNMe(3))(MeCalix) (6) via a net isomerization reaction which was found to be catalytic in MeI. The corresponding reaction of 3 with CD(3)I gave Ti(NNMe(2)CD(3))(MeCalix) (6-d(3)) with concomitant elimination of MeI. Reaction of 3 with 1 equiv of MeOTf gave [Ti(NNMe(3))(Me(2)Calix)][OTf] (7-OTf) which in turn reacted with (n)Bu(4)NI to form 6 and MeI. Addition of PhCHO to 3 gave the mu-oxo dimer [Ti(mu-O)(Me(2)Calix)](2) and benzaldehyde-dimethylhydrazone. Reaction of either 3 or 6 with (t)BuNCO gave the zwitterionic species Ti{(t)BuNC(NNMe(3))O}(MeCalix) (10) which has been crystallographically characterized. Compound 10 is the formal product of insertion of an isocyanate into the Ti=N(alpha) bond of a titanium hydrazide or hydrazidium species (Me(2)Calix or MeCalix = dianion or trianion of the di- or monomethyl ether of p-tert-butyl calix[4]arene, respectively).

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The competitive formation mechanism of N-nitrosodimethylamine and formaldehyde dimethylhydrazone from 1,1-dimethylhydrazine during ozonation in air: A combined theoretical and experimental study

et al. 2019

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Molecular structure of 1,1-dimethylhydrazine

Cited by 3 publications

References 10 publications

Reactions of Cyclopentadienyl−Amidinate Titanium Hydrazides with CO₂, CS₂, and Isocyanates: Ti═N_α Cycloaddition, Cycloaddition−Insertion, and Cycloaddition−NNR₂ Group Transfer Reactions

Reactions of Cyclopentadienyl−Amidinate Titanium Hydrazides with CO₂, CS₂, and Isocyanates: Ti═N_α Cycloaddition, Cycloaddition−Insertion, and Cycloaddition−NNR₂ Group Transfer Reactions

Synthesis, Structures and Reactivity of Group 4 Hydrazido Complexes Supported by Calix[4]arene Ligands

The competitive formation mechanism of N-nitrosodimethylamine and formaldehyde dimethylhydrazone from 1,1-dimethylhydrazine during ozonation in air: A combined theoretical and experimental study

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Molecular structure of 1,1-dimethylhydrazine

Cited by 3 publications

References 10 publications

Reactions of Cyclopentadienyl−Amidinate Titanium Hydrazides with CO2, CS2, and Isocyanates: Ti═Nα Cycloaddition, Cycloaddition−Insertion, and Cycloaddition−NNR2 Group Transfer Reactions

Reactions of Cyclopentadienyl−Amidinate Titanium Hydrazides with CO2, CS2, and Isocyanates: Ti═Nα Cycloaddition, Cycloaddition−Insertion, and Cycloaddition−NNR2 Group Transfer Reactions

Synthesis, Structures and Reactivity of Group 4 Hydrazido Complexes Supported by Calix[4]arene Ligands

The competitive formation mechanism of N-nitrosodimethylamine and formaldehyde dimethylhydrazone from 1,1-dimethylhydrazine during ozonation in air: A combined theoretical and experimental study

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Reactions of Cyclopentadienyl−Amidinate Titanium Hydrazides with CO₂, CS₂, and Isocyanates: Ti═N_α Cycloaddition, Cycloaddition−Insertion, and Cycloaddition−NNR₂ Group Transfer Reactions

Reactions of Cyclopentadienyl−Amidinate Titanium Hydrazides with CO₂, CS₂, and Isocyanates: Ti═N_α Cycloaddition, Cycloaddition−Insertion, and Cycloaddition−NNR₂ Group Transfer Reactions