Triorganotin cations stabilized by intramolecular SnN coordination; synthesis and characterization of {C,N,N′-2,6-bis[(dimethylamino)methyl]phenyl}diorganotin bromides

Koten, Gerard van; Jastrzebski, Johann T. B. H.; Noltes, J. G.; Spek, Anthony L.; Schoone, J. C.

doi:10.1016/s0022-328x(00)90980-x

Cited by 151 publications

(72 citation statements)

References 9 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…This is corroborated by earlier results from studies of the selective lithiation of NC(H)N (i.e. the achiral version of 2; see Scheme 2, R H) [41]. Significant lithiation of the thermodynamically less stabilized ortho,ortho% position was noted in Et 2 O, whereas in hexane intramolecular nitrogen-assistance by both CH 2 NMe 2 groups directed the regioselectivity, hence giving ortho,ortho-lithiation exclusively.…”

Section: Lithiation Of Oxo-functionalized Chiral Pincer Ligandssupporting

confidence: 82%

Chiral platinum and palladium complexes containing functionalized C2-symmetric bisaminoaryl ‘Pincer’ ligands

Albrecht

Kocks

Spek

et al. 2001

Journal of Organometallic Chemistry

Self Cite

View full text Add to dashboard Cite

Dedicated to Professor Jean Normant on the occasion of his 65th anniversary in admiration of his great contribution to the application of organocopper chemistry. AbstractThe synthesis of enantiopure (oxo-functionalized) C 2 -symmetric NCN pincer ligands is described. A key step is the symmetric functionalization of the benzylic positions, which was achieved by enantioselective ketone reduction and subsequent stereoselective substitution protocols. The introduction of a-alkyl substituents has a pronounced effect on the cavity for metal binding. For example, lithiation of the a-ethyl-functionalized pincer ligand afforded mixed (alkyl)(aryl)lithium aggregates rather than dinuclear bis(aryl) lithium [Li(NCN)] 2 species as usually observed for NCN-lithium complexes. Similar effects were established for the (trans)-metalation reaction, which proceeded significantly slower when the steric demand of the a-substituent is increased. The potential of the corresponding enantiopure palladium and ruthenium complexes as enantioselective catalyst has been probed in the asymmetric aldol condensation and hydrogen transfer reactions. The low enantiomeric excess of the products of both reactions indicated that face-discrimination of substrates is not induced by these catalysts and that the chiral information must be located in closer proximity to the metal center.

show abstract

Section: Lithiation Of Oxo-functionalized Chiral Pincer Ligandssupporting

confidence: 82%

Chiral platinum and palladium complexes containing functionalized C2-symmetric bisaminoaryl ‘Pincer’ ligands

Albrecht

Kocks

Spek

et al. 2001

Journal of Organometallic Chemistry

Self Cite

View full text Add to dashboard Cite

show abstract

“…The molecular structure determination of compound 5 (Fig. 5, Table 1) confirmed the prediction of a distorted trigonal bipyramidal structure with organic groups and one of the halides in the equatorial and second halide and nitrogen donor in axial positions previously predicted by van Koten et al 22 The nitrogen atom is more strongly bonded to tin than in the corresponding diorganotin dihalides 2 and 4. The Sn-N bond distance (2.444(5)Å) is comparable to the same type distances in triorganotin compounds having this or similar types of ligand 16 and 1.…”

Section: Structure Of 1-5supporting

confidence: 83%

Structure and properties of double-C,N-chelated tri- and diorganotin(IV) halides

Novák

Padělková

Kolářová

et al. 2005

Appl. Organometal. Chem.

View full text Add to dashboard Cite

show abstract

“…It is noteworthy that in Cp(2-Me2NCH2C6H4)2Ti2' and C P~(~-M~~N C H~C~H~) T~~~~ the corresponding N-Ti-C angles are 73.4 and 73°,22b respectively, indicating that the bite of the bidentate benzylamino ligand has a rather constant value.23 Also in ionic {2,6-(Me*NCH2)2C6H3)Me2Sn+Br-, the structure of which recently has been elucidated, the N-Sn-C angles in the two five-membered chelate rings are about 75°. 26 The five-membered chelate ring is puckered a t the C N S n part both in I1 and in IV. The two ring conformers of I1 have equal stability.…”

Section: Discussionmentioning

confidence: 99%

Synthesis of C,Sn-chiral triorganotin halides via C-chiral arylcopper and arylgoldlithium intermediates. Crystal and molecular structure of one [2-[1-(S)-(dimethylamino)ethyl]phenyl]methylphenyltin bromide diastereomer

Koten¹,

Jastrzebski²,

Noltes³

et al. 1978

J. Am. Chem. Soc.

Self Cite

130

View full text Add to dashboard Cite

Abstract:The crystal and molecular structure and absolute configuration of 2-[ l-(S)-Me2NCH(Me)]C6H4SfnMePhBr, which is the first example of a diastereomerically pure chiral triorganotin halide, are determined by a single-crystal x-ray diffraction study. Crystals are orthorhombic, space group P212121 with Z = 4 in a unit cell of dimensions n = 9.370 (4), b = 13.361 (3), and c = 14.283 (4) A. The final R value is 0.048 for 2784 reflections. The tin atom has a distorted trigonal bipyramidal geometry with the C,N-bonded Me2NCH(Me)C6H4 group spanning one equatorial (C) and one axial (N) site. The Ph and M e groups reside in the two equatorial positions resulting in an (S)sn configuration at the tin atom (cf. Figure 1). The configuration at Sn was unambiguously determined by using anomalous diffraction effects which likewise resulted in an independent check of the configuration at the CY-C atom (S configuration). The

show abstract

Triorganotin cations stabilized by intramolecular SnN coordination; synthesis and characterization of {C,N,N′-2,6-bis[(dimethylamino)methyl]phenyl}diorganotin bromides

Cited by 151 publications

References 9 publications

Chiral platinum and palladium complexes containing functionalized C2-symmetric bisaminoaryl ‘Pincer’ ligands

Chiral platinum and palladium complexes containing functionalized C2-symmetric bisaminoaryl ‘Pincer’ ligands

Structure and properties of double-C,N-chelated tri- and diorganotin(IV) halides

Synthesis of C,Sn-chiral triorganotin halides via C-chiral arylcopper and arylgoldlithium intermediates. Crystal and molecular structure of one [2-[1-(S)-(dimethylamino)ethyl]phenyl]methylphenyltin bromide diastereomer

Contact Info

Product

Resources

About