Intramolecular Coordination in Organometallic Compounds of Groups 2, 12, and 13

Gruter, Gert Jan M.; Klink, Gerard P. M. van; Akkerman, Otto S.; Bickelhaupt, F.

doi:10.1021/cr00039a006

Cited by 78 publications

(31 citation statements)

References 129 publications

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“…31°C kristallisieren. Nach la È ngerem Aufbewahren bei Raumtemperatur nimmt die Viskosita È t der flu È ssigen Verbindungen zu; sie lo È sen sich nur noch schwer, teilweise nicht mehr vollsta Èn-dig in den ga È ngigen Lo È semitteln und zeigen einen deutlich erniedrigten Dampfdruck, was auf eine koordinative Oligomerisierung [19] (2); Al±C(6) 1,992 (2); Al±N 2,057(2); C(1)±Al±C (5) Ein Vergleich der Luftempfindlichkeiten der dargestellten 3-(Dimethylamino)propylaluminiumderivate Me 2±n Cl n Al(CH 2 ) 3 NMe 2 mit n = 0 (1), 1 (14) und 2 (8) untereinander weist mit der mit steigender ChlorSubstitution deutlich zunehmenden Stabilita È t der Verbindungen auf eine sta È rker werdende N ® Al-Bindung aufgrund zunehmender Akzeptorwirkung des Aluminiums. Die Molmassenbestimmung an der Monochlorverbindung 14 zeigt ± ebenso wie fu È r das Dichlorderivat 6 ± in Lo È sung Monomere.…”

Section: Ergebnisse Und Diskussionunclassified

“…Durch diese Beobachtung wird ein assoziativer Prozeû ho È herer molekularer Ordnung in konzentrierter Lo È -sung nahegelegt ± unter Beibehaltung der Koordinationszahl von 4 am Aluminium, wie konzentrationsabha È ngige 27 Al-NMR-Messungen zeigen. Øhnliches wurde fu È r 3-Aminopropylmagnesiumderivate diskutiert [19].…”

Section: Multikern-nmr-spektroskopische Untersuchungenunclassified

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Synthese, Röntgenstrukturanalyse und Multikern-NMR-spektroskopische Untersuchung einiger intramolekular stickstoffstabilisierter Bor-, Aluminium- und Galliumorganyle

Schumann

Wassermann

Schutte

et al. 2000

Z. anorg. allg. Chem.

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Die intramolekular stickstoffstabilisierten Organoaluminium‐ und Organoborverbindungen Me2Al‐ (CH2)3NMe2 (1), Me2AlC10H6‐8‐NMe2 (2), iPr2Al(CH2)3NEt2 (3), (CH2)5Al(CH2)3NMe2 (4) und (CH2)5B(CH2)3NMe2 (5) werden aus Me2AlCl und den entsprechenden Lithiumorganylen bzw. aus AlCl3 oder BCl3, dem Lithiumalkyl und iPrMgCl oder BrMg(CH2)5MgBr erhalten. AlCl3 und GaCl3 reagieren mit LiCH2CHMeCH2NMe2 bzw. Li(CH2)3NMe2 unter Bildung von Cl2AlCH2CHMeCH2NMe2 (6) bzw. Cl2Al(CH2)3NMe2 (8) und Cl2Ga(CH2)3NMe2 (9). Bei der Umsetzung von 6 bzw. 8 oder 9 mit BrMg(CH2)5MgBr bzw. BrMg(CH2)6MgBr entstehen (CH2)5AlCH2CHMeCH2NMe2 (7) bzw. (CH2)6Al(CH2)3NMe2 (10) und (CH2)6Ga(CH2)3NMe2 (11). Das durch Komproportionierung aus AlCl3 und Me2AlCl erhaltene MeAlCl2 reagiert mit 2 Äquivalenten Li(CH2)3NMe2 zu MeAl[(CH2)3NMe2]2 (12) und mit MeN[(CH2)3MgCl]2 unter Bildung von MeAl[(CH2)3]2NMe (13). Entsprechend reagieren MeAlCl2 oder MeGaCl2 bzw. GaCl3 mit einem Äquivalent Lithiumorganyl zu den intramolekular stickstoffstabilisierten Organoaluminium‐ und Organogalliumchloriden MeClAl(CH2)3NMe2 (14), MeClGa(CH2)3NMe2 (15), MeClGaC6H4‐2‐CH2NMe2 (16) und Cl2GaC6H4‐2‐CHMeNMe2 (17). Die Verbindungen wurden durch Elementaranalysen, 1H‐, 11B‐, 13C‐ und 27Al‐NMR‐Untersuchungen sowie massenspektrometrisch charakterisiert. Die Einkristall‐Röntgenstrukturanalysen von 1, 2, 4, 5 und 17 zeigen die monomeren Molekülstrukturen mit intramolekularer Stickstoff‐Koordination.

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Section: Ergebnisse Und Diskussionunclassified

Section: Multikern-nmr-spektroskopische Untersuchungenunclassified

Synthese, Röntgenstrukturanalyse und Multikern-NMR-spektroskopische Untersuchung einiger intramolekular stickstoffstabilisierter Bor-, Aluminium- und Galliumorganyle

Schumann

Wassermann

Schutte

et al. 2000

Z. anorg. allg. Chem.

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“…A number of complexes with different transition metals have been isolated; that is, manganese, cobalt, molybdenum, and tungsten. 59 The crystal structure of Me 2 N(CH 2 ) 3 ZnW(Cp)(CO) 3 , determined by X-ray crystallography, shows a tricoordinate zinc atom with a zinc -tungsten bond distance of 2.685Å. TM = Mn(CO) 5 , Co(CO) 4 , CpMo(CO) 3 , CpW(CO) 3 .…”

Section: Table 12mentioning

confidence: 99%

Zinc: Organometallic ChemistryBased in part on the article Zinc: Organometallic Chemistry by Gerard Parkin which appeared in theEncyclopedia of Inorganic Chemistry, First Edition.

Gr��vy¹

2005

Encyclopedia of Inorganic Chemistry

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Since the discovery of the first organozinc compounds by Sir Edward Frankland in 1849, the organometallic chemistry of zinc made remarkable advances and organozinc species have become essential tools for organic chemists. During the past decade, numerous new and modified procedures for the preparation of the title compounds have been published, rendering their synthesis easier, faster, and less expensive and giving higher yields. The coordination chemistry of organozinc derivatives has been subject of further interest and various intra‐ and intermolecular complexes with different donor ligands have been structurally characterized by X‐ray crystallography and spectroscopic methods. The accumulation of molecular structures, physicochemical studies, and computational calculations has led to a better understanding of the organozinc chemistry, and consequently to the design of new derivatives for specific applications. Even if the development of areas like the chemistry of organozinc anions and cations is still in its early stage, these compounds, which exhibit properties different than those of the parent organometallic species, appear to have promising applications in synthesis and catalytic reactions. During the past ten years, the chemistry of organo‐ gem ‐dizincio derivatives has also been the subject of much interest and progress. These reagents can form two carbon–carbon bonds in a one‐pot reaction and with high stereoselectivity. They became key reagents for organic chemists who want to combine multiple transformations in one operation. The importance of organometallic compounds of zinc can be seen in the growing number of their applications in synthesis. They are used in many reactions such as substitutions, additions to carbonyl compounds and unsaturated systems, cyclopropanations, and polymerizations. Furthermore, as a result of their low reactivity, they tolerate a wide variety of functionalities and perform most of the transformations with high regio‐ and enantioselectivity. After spending more than half a century in the shade of Grignard and organolithium reagents, organozinc reagents are becoming more and more important in modern chemistry.

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“…[36][37][38][39][40][41][42]. This chapter will deal specifically with pincer ligands of the Group 1 elements (Li, Na) with some relationships drawn to the complexes of Mg, Cu and Zn where appropriate [43]. This monograph is not intended as a complete review of all compounds of the title elements that could be labelled as containing a pincer ligand.…”

Section: Introductionmentioning

confidence: 99%

“…Note that "E" can also be formally anionic applications in the synthesis of other metal and non-metal pincer derivatives. Hence, metal metathesis reactions are their main use; this aspect has been discussed previously [38,43].…”

Section: Introductionmentioning

confidence: 99%

Pincer Complexes of Lithium, Sodium, Magnesium and Related Metals: A Discussion of Solution and Solid-State Aggregated Structure and Reactivity

Gossage

2015

The Privileged Pincer-Metal Platform: Coordination Chemistry &Amp; Applications

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Intramolecular Coordination in Organometallic Compounds of Groups 2, 12, and 13

Cited by 78 publications

References 129 publications

Synthese, Röntgenstrukturanalyse und Multikern-NMR-spektroskopische Untersuchung einiger intramolekular stickstoffstabilisierter Bor-, Aluminium- und Galliumorganyle

Synthese, Röntgenstrukturanalyse und Multikern-NMR-spektroskopische Untersuchung einiger intramolekular stickstoffstabilisierter Bor-, Aluminium- und Galliumorganyle

Zinc: Organometallic ChemistryBased in part on the article Zinc: Organometallic Chemistry by Gerard Parkin which appeared in theEncyclopedia of Inorganic Chemistry, First Edition.

Pincer Complexes of Lithium, Sodium, Magnesium and Related Metals: A Discussion of Solution and Solid-State Aggregated Structure and Reactivity

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