“…Previous heteroallene insertion reactions , of zinc alkyl amido complexes inserted into the Zn−N bond yielding dimeric and oligomeric bridged complexes; thus the reaction exhibited by 2 is unique. The reaction of isocyanate with 2 is also different from the reactions of isocyanates with β-ketoimines and β-dicarbonyls; in these cases the methine hydrogen atom was replaced and an amine was formed. − …”
mentioning
confidence: 99%
“…The reaction of isocyanate with 2 is also different from the reactions of isocyanates with β-ketoimines and β-dicarbonyls; in these cases the methine hydrogen atom was replaced and an amine was formed. [39][40][41] Complex 3 was isolated as a colorless crystalline solid sensitive to air and moisture. The Infrared spectrum showed strong absorptions at 1611, 1603 cm -1 and at 1297 cm -1 due to the CdO and PdN stretching vibrations.…”
Reaction of dimethyl zinc with bis{trimethylsilyliminodi(phenyl)phosphorano}methane,
H2C(Ph2PNSiMe3)2 (1), in toluene gave the alkyl zinc
complex [ZnMe{HC(Ph2PNSiMe3)2-κ
2
N,N
‘}] (2) via
elimination of methane. The crystal structure of the
complex confirms its monomeric nature and the bidentate coordination of the bis(iminophosphorano)methanide
ligand to the zinc. AdNCO (Ad = adamantyl) reacted
smoothly with 2 via a nucleophilic addition forming a
new C−C bond in the novel tripodal alkyl zinc complex,
[ZnMe{HC{C(O)N(Ad)}(Ph2PNSiMe3)2-κ
3
N,N
‘
,N"}], 3.
The methine carbon atom resonances (δ 28.4 for 2 and
52.9 for 3) were observed as triplets due to the coupling
to two equivalent phosphorus atoms. The crystal structure of 3 shows a propeller type arrangement with the
three nitrogen atoms of the monoanionic tridentate
ligand bound to zinc.
“…Previous heteroallene insertion reactions , of zinc alkyl amido complexes inserted into the Zn−N bond yielding dimeric and oligomeric bridged complexes; thus the reaction exhibited by 2 is unique. The reaction of isocyanate with 2 is also different from the reactions of isocyanates with β-ketoimines and β-dicarbonyls; in these cases the methine hydrogen atom was replaced and an amine was formed. − …”
mentioning
confidence: 99%
“…The reaction of isocyanate with 2 is also different from the reactions of isocyanates with β-ketoimines and β-dicarbonyls; in these cases the methine hydrogen atom was replaced and an amine was formed. [39][40][41] Complex 3 was isolated as a colorless crystalline solid sensitive to air and moisture. The Infrared spectrum showed strong absorptions at 1611, 1603 cm -1 and at 1297 cm -1 due to the CdO and PdN stretching vibrations.…”
Reaction of dimethyl zinc with bis{trimethylsilyliminodi(phenyl)phosphorano}methane,
H2C(Ph2PNSiMe3)2 (1), in toluene gave the alkyl zinc
complex [ZnMe{HC(Ph2PNSiMe3)2-κ
2
N,N
‘}] (2) via
elimination of methane. The crystal structure of the
complex confirms its monomeric nature and the bidentate coordination of the bis(iminophosphorano)methanide
ligand to the zinc. AdNCO (Ad = adamantyl) reacted
smoothly with 2 via a nucleophilic addition forming a
new C−C bond in the novel tripodal alkyl zinc complex,
[ZnMe{HC{C(O)N(Ad)}(Ph2PNSiMe3)2-κ
3
N,N
‘
,N"}], 3.
The methine carbon atom resonances (δ 28.4 for 2 and
52.9 for 3) were observed as triplets due to the coupling
to two equivalent phosphorus atoms. The crystal structure of 3 shows a propeller type arrangement with the
three nitrogen atoms of the monoanionic tridentate
ligand bound to zinc.
“…Such a dependence was observed in the reactivity of [Ni(acacen)] and [Cu(acacen)] with various electrophiles. 6 We cannot exclude, however, that the nitrosation of the acacen ligand in [Fe(acacen)] may be a metalassisted transfer of NO from the metal to the ligand. We thank N.S.F.…”
Reaction of nitric oxide with N,N'-ethylenebis(acetylacetoneiminato)iron(ii), [Fe(acacen)], led to a mixed-valence tetranuclear iron complex, { [ON-Fe{a~acen(NO)~}]~Fe}, containing, as seen from the X-ray analysis, three ironnitrosyl complexes binding the fourth iron in an octahedral cavity with six oxygen donor atoms.Reaction of NO with transition metal chelate and macrocyclic complexes is quite straightforward and leads to the corresponding metal-nitrosyl derivatives. 1,2 Such a class of compounds is interesting for a variety of reason^.^ In particular, the iron-Schiff base complexes containing a nitrosyl group have been extensively studied for their peculiar magnetic properties.4 Their synthesis was performed by the normal methodology, reacting NO with the iron(r1)-Schiff base complex.We found, however, that the reaction of NO with N , N 'ethylenebis(acetylacetoneiminato)iron(r~), [Fe(acacen)], (1), is very complex and occurs both at the metal and at the ligand ending with a polymetallic aggregate. The unique nature of the reaction is shown by the fact that [Fe(salen)]4 [salen = N,N'-ethylenebis(salicylaldiminato)dianion] and substituted [Fe(acacen)]2 undergo normal nitrosation at the metal. The synthesis of (1) was recently reported,5 and the complex was found to be soluble in aromatic hydrocarbons and monomeric in solution. A toluene or tetrahydrofuran solution of (1) was reacted with NO at room temperature. A few hours later, complex (2) separated from the solution as black crystals (ca.
“…The results of metal-nitroxyl interaction studies are pertinent to a wide variety of nitroxyl spin label and spin probe investigations. 13 We are investigating a wide range of complexes containing both a paramagnetic metal and a nitroxyl free radical. Among our recent demonstrations of resolved electron-electron spin-spin splitting in electron paramagnetic resonance (EPR) spectra we reported compound I.lb In this paper we report III, = 3, R = Ph the synthesis and EPR spectra of II, in which the ethylene bridge of I has been replaced by a trimethylene bridge yielding a unique opportunity to observe metal electron-nitroxyl electron coupling for two isomers of a compound.…”
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