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Cation-induced structural alterations in the organo alkali metal derivatives of triphenylmethane: a combined x-ray and NMR study of the potassium-cesium salts

Cation-induced structural alterations in the organo alkali metal derivatives of triphenylmethane:... Organometallics 1993,12, 1193-1200 Cation-Induced Structural Alterations in the Organo Alkali Metal Derivatives of Triphenylmethane: Combined X-ray and NMR Study of the K-Cs Salts Daniele Hoffmann,? Walter Bauer,t Paul von Ragu6 Schleyer,**+ Ursula Pieper,$ and Dietmar Stalkei Institute of Organic Chemistry, Friedrich- Alexander- Universitat Erlangen-Niirnberg, Henkestrasse 42, W-8520 Erlangen, Germany and the Institute of Inorganic Chemistry, Georg-August- Universitat Gottingen, Tammanstrasse 4, W-3400 Gbttingen, Germany Received September 29, 1992 The set of alkali metal solid-state structures of Ph3CM-nL [M = K, Rb, Cs; L = (ligands) PMDTA (N,ZV,”JV”JV”-pentamethyldiethylenetriamine), THF (tetrahydrofuran)] provides instructive comparisons. Ph3CK-THF-PMDTA (1) crystallizes as a monomeric contact ion pair: the K+ cation is symmetrically $-coordinated to one of the phenyl rings, but not to the deprotonated central carbon. Both [Ph&Rb-PMDTA]. (2) and [P~~CCWPMDTA]. (3) form one-dimensional polymers and eschew THF. The Rb cations in 2 bridge the triphenylmethyl moieties by +x“%xmtion to separate phenyl rings. This gives rise to a zigzag chain. In 3, each Cs cation also bridges two carbanions, but in a somewhat different fashion. While Cs+ is located rather symmetrically (119 above the phenyl ring of one trityl moiety, a.“propeller”-like coordination to a second trityl anion involves contacts with all three phenyl rings as well http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Organometallics Unpaywall

Cation-induced structural alterations in the organo alkali metal derivatives of triphenylmethane: a combined x-ray and NMR study of the potassium-cesium salts

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0276-7333
DOI
10.1021/om00028a038
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Abstract

Organometallics 1993,12, 1193-1200 Cation-Induced Structural Alterations in the Organo Alkali Metal Derivatives of Triphenylmethane: Combined X-ray and NMR Study of the K-Cs Salts Daniele Hoffmann,? Walter Bauer,t Paul von Ragu6 Schleyer,**+ Ursula Pieper,$ and Dietmar Stalkei Institute of Organic Chemistry, Friedrich- Alexander- Universitat Erlangen-Niirnberg, Henkestrasse 42, W-8520 Erlangen, Germany and the Institute of Inorganic Chemistry, Georg-August- Universitat Gottingen, Tammanstrasse 4, W-3400 Gbttingen, Germany Received September 29, 1992 The set of alkali metal solid-state structures of Ph3CM-nL [M = K, Rb, Cs; L = (ligands) PMDTA (N,ZV,”JV”JV”-pentamethyldiethylenetriamine), THF (tetrahydrofuran)] provides instructive comparisons. Ph3CK-THF-PMDTA (1) crystallizes as a monomeric contact ion pair: the K+ cation is symmetrically $-coordinated to one of the phenyl rings, but not to the deprotonated central carbon. Both [Ph&Rb-PMDTA]. (2) and [P~~CCWPMDTA]. (3) form one-dimensional polymers and eschew THF. The Rb cations in 2 bridge the triphenylmethyl moieties by +x“%xmtion to separate phenyl rings. This gives rise to a zigzag chain. In 3, each Cs cation also bridges two carbanions, but in a somewhat different fashion. While Cs+ is located rather symmetrically (119 above the phenyl ring of one trityl moiety, a.“propeller”-like coordination to a second trityl anion involves contacts with all three phenyl rings as well

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Organometallics – Unpaywall

Published: Apr 1, 1993

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