“…According to the 1 H NMR spectra in toluene- d 8 in the temperature range from 185 to 345 K, both 1 and 1(thf) coexist with two minor species in a temperature-independent molar ratio of approximately 24:1:1. The resonances of the minor species are identical to those of Zn(C 6 H 4 CH 2 NMe 2 -2) 2 and the 2:1 zincate 2 , suggesting the existence of equilibrium 1 in solution, eq 1. …”
Section: Resultsmentioning
confidence: 78%
“…All standard chemicals were purchased from Aldrich Chemical Co. and Acros and used as received. [Li(C 6 H 4 CH 2 NMe 2 -2)] 4 , Zn(C 6 H 4 CH 2 NMe 2 -2) 2 , and LiCH 2 SiMe 3 were prepared by published procedures. 1 H and 13 C NMR spectra were recorded at 200 and 50 MHz at room temperature, unless stated otherwise.…”
Homoleptic lithium zincates with intramolecular Li-N coordination, i.e., Li(thf) n Zn-(C 6 H 4 CH 2 NMe 2 -2) 3 (n ) 0 (1); n ) 1 (1(thf))) and Li 2 Zn(C 6 H 4 CH 2 NMe 2 -2) 4 (2) have been prepared by reacting [Li(C 6 H 4 CH 2 NMe 2 -2)] 4 with Zn(C 6 H 4 CH 2 NMe 2 -2) 2 . In the solid state 1(thf) is a monomer containing a distorted tetrahedral zinc atom. The zinc is surrounded by three monoanionic C 6 H 4 CH 2 NMe 2 -2 (dmba) ligands, which all show a different bonding mode: η 1 -C bonding to zinc and nitrogen coordination to lithium; η 1 ,µ 2 -C bridge bonding to zinc and lithium with Li-N coordination; and C,N-chelate bonded to zinc. One thf coordinates to lithium. In the solid state, 2 is a monomeric dilithium tetraarylzincate complex containing a tetrahedral zinc atom. The four dmba ligands are all similarly η 1 ,µ 2 -C bridgebonded to zinc and lithium, and each lithium is four-coordinate by two additional Li-N bonds. The reaction of LiCH 2 SiMe 3 and Zn(C 6 H 4 CH 2 NMe 2 -2) 2 did not give a mixed zincate complex but the respective homoleptic zincate complexes instead. Both homoleptic and in situ prepared mixed zincate complexes react readily with 2-cyclohexen-1-one, but the product composition shows that the in situ prepared zincate disproportionates into the corresponding homoleptic zincates prior to reaction.
“…According to the 1 H NMR spectra in toluene- d 8 in the temperature range from 185 to 345 K, both 1 and 1(thf) coexist with two minor species in a temperature-independent molar ratio of approximately 24:1:1. The resonances of the minor species are identical to those of Zn(C 6 H 4 CH 2 NMe 2 -2) 2 and the 2:1 zincate 2 , suggesting the existence of equilibrium 1 in solution, eq 1. …”
Section: Resultsmentioning
confidence: 78%
“…All standard chemicals were purchased from Aldrich Chemical Co. and Acros and used as received. [Li(C 6 H 4 CH 2 NMe 2 -2)] 4 , Zn(C 6 H 4 CH 2 NMe 2 -2) 2 , and LiCH 2 SiMe 3 were prepared by published procedures. 1 H and 13 C NMR spectra were recorded at 200 and 50 MHz at room temperature, unless stated otherwise.…”
Homoleptic lithium zincates with intramolecular Li-N coordination, i.e., Li(thf) n Zn-(C 6 H 4 CH 2 NMe 2 -2) 3 (n ) 0 (1); n ) 1 (1(thf))) and Li 2 Zn(C 6 H 4 CH 2 NMe 2 -2) 4 (2) have been prepared by reacting [Li(C 6 H 4 CH 2 NMe 2 -2)] 4 with Zn(C 6 H 4 CH 2 NMe 2 -2) 2 . In the solid state 1(thf) is a monomer containing a distorted tetrahedral zinc atom. The zinc is surrounded by three monoanionic C 6 H 4 CH 2 NMe 2 -2 (dmba) ligands, which all show a different bonding mode: η 1 -C bonding to zinc and nitrogen coordination to lithium; η 1 ,µ 2 -C bridge bonding to zinc and lithium with Li-N coordination; and C,N-chelate bonded to zinc. One thf coordinates to lithium. In the solid state, 2 is a monomeric dilithium tetraarylzincate complex containing a tetrahedral zinc atom. The four dmba ligands are all similarly η 1 ,µ 2 -C bridgebonded to zinc and lithium, and each lithium is four-coordinate by two additional Li-N bonds. The reaction of LiCH 2 SiMe 3 and Zn(C 6 H 4 CH 2 NMe 2 -2) 2 did not give a mixed zincate complex but the respective homoleptic zincate complexes instead. Both homoleptic and in situ prepared mixed zincate complexes react readily with 2-cyclohexen-1-one, but the product composition shows that the in situ prepared zincate disproportionates into the corresponding homoleptic zincates prior to reaction.
“…In this respect it is rather surprising that only a few diorganozinc compounds have been reported in which intramolecular coordination of a heteroatom-containing substituent is present. Although the synthesis of (2-Me 2 NCH 2 C 6 H 4 ) 2 Zn (65) was reported already in 1984 117 and it was suggested that, based on the observed 1 H NMR spectra, both nitrogen substituents are involved in nitrogen-zinc coordination, its structure in the solid state has not been established by X-ray crystallography.…”
Introduction
Organozincates
Dialkyl‐ and Diarylzinc Compounds
Heteroleptic
RZn
Y
Compounds
Organozinc Compounds Containing a Zinc–Transition Metal Bond
Conclusions
“…Infrared spectra were run on a Beckman IR-12 spectrometer, using KBr or Csl cells, and mass spectra on a Varian MAT CH-5DF instrument operating in the field desorption (FD) or electron impact (El) modes. The lithiation of (dimethy1amino)methylbenzene (HL) followed the procedure described elsewhere (4,5).…”
Section: Methodsmentioning
confidence: 99%
“…2, 15, and references therein). The electron impact (El) mass spectrum of LBr, taken from an earlier publication (5) shows that the principal ion is C7H7Brt, with CSHl2Nt, CsHIONt, and C2Hqt as the other important species. The spectrum of L21nCl in the same mode is quite different, with C2Hat as the principal ion.…”
Section: Nuclear Magnetic Resonance Spectroscopymentioning
The syntheses of the arylindium compounds L2InX (X = Cl, I), L2InR (R = CH3, C6H5), L3In and L2InSnPh3 (L = 2-[(dimethylamino)methyl]phenyl) are reported. The pathway of the redistribution reactions involving InCl3 and L3In are discussed. Mass and 1H nmr spectra are reported.
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