Derivate des Borabenzols, VIII: Ein neuer Weg zu Alkalimetallborinaten. Synthesen von Ruthenium‐, Osmium‐, Rhodium‐ und Platin‐Verbindungen mit Borinat‐Liganden

Herberich, Gerhard E.; Becker, Hans Jürgen; Carsten, Klaus; Engelke, Cordula; Koch, W.

doi:10.1002/cber.19761090704

Cited by 52 publications

(15 citation statements)

References 21 publications

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“…3(16) 129.9 (14) 151.6 (13) 138.1 ( l G ) 145.1 (17) 141.3(12) 128.6 ( 1 4 ) 152.1 (13) 141.6 (12) 151.5 (15) 135.3 ( 1 2 ) 130. 6 (12) 139.6 (13) 136.5 (14) 137.…”

Section: -C(14)mentioning

confidence: 97%

Synthese und Strukturuntersuchung von Pyridin‐Borabenzol und Pyridin‐2‐Boranaphthalin

et al. 1985

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Die Synthese von Pyridin-Borabenzol (8) gelingt, wenn aus 1 -Methoxy-6-(trimethylsilyl)-l-bora-2,4-cyclohexadien (7) in Gegenwart von Pyridin bei 60°C Methoxytrimethylsilan abgespalten wird. Die gelbe Verbindung zeigt eine Charge-Transfer-Bande bei 472 nm. Die Rontgenstrukturanalyse sowie die Protonensignale von 8 belegen den aromatischen Charakter des Borabenzols. Pyridin-und Borabenzolring sind um 43.3" gegeneinander verdreht. Pyridin-2-Boranaphthalin (14a), dessen Herstellung durch Abspaltung von Chlortrimethylsilan in Gegenwart von Pyridin aus 2-Chlor-i ,2-dihydro-I -(trimethylsilyl)-2-boranaphthalin (13) erfolgt, bildet tiefrote Kristalle. Seine Charge-Transfer-Bande bei 486 nm kommt ebenso wie diejenige in 8 durch einen ubergang aus dem HOMO des Boraaren-Molekulteils in das LUMO des Pyridinteils zustande. Die geringe Verdrillung der beiden Ringsysteme in 14a von 8.1 O erleichtert den Elektronentransfer. Die Konjugation der beiden Molekulteile in 14a fuhrt gegenuber 8 zu einer Verkurzung der B-N-Bindung von 155.8 auf 151.5 pm. Im Gegensatz zum roten 14a ist Triethylamin-2-Boranaphthalin (14b) farblos. Synthesis and Structure Investigation of Pyridine-Borabenzene and Pyridine-2-BoranaphthaleneThe synthesis of pyridine-borabenzene (8) succeeds when methoxytrimethylsilane is eliminated from l-methoxy-6-(trimethylsilyl)-l-bora-2,4-cyclohexadiene (7) in the presence of pyridine at 60°C. The yellow compound shows a charge transfer band at 472 nm. The X-ray structure analysis as well as the proton NMR signals of 8 prove the aromatic character of the borabenzene. Pyridine and borabenzene ring are twisted by 43.3". Pyridine-2-boranaphthalene (14a), whose synthesis occurs by elimination of chlorotrimethylsilane from 2-chloro-l,2-dihydro-l -(trimethylsilyl)-2-boranaphthalene (13) in the presence of pyridine, forms deep red crystals. Its charge transfer band at 486 nm results like that in 8 by a transition from the HOMO of the boraarene part of the molecule into the LUMO of the pyridine part. The small twist of the two ring systems in 14a of 8.1" facilitates the electron transfer. The conjugation of both parts of the molecule in 14a leads to a shortening of the B-N-bond compared with 8 from 155.8 to 151.5 pm. In contrast to the red 14a, triethylamine-2-boranaphthalene (14 b) is colourless.Obwohl die Bor-Kohlenstoff-Doppelbindung nicht der klassischen Doppelbindungsregel widerspricht, sind bis heute weder das Borabenzol selbst, noch andere Boraarene bekanntgeworden. Herberich 1) schreibt dem Borabenzol 1 (Borini), Borixinz), Borinina)) einen hochreaktiven 0 VCH Verlagsgesellschaft mbH, D-6940 Weinheim, 1985

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“…3(16) 129.9 (14) 151.6 (13) 138.1 ( l G ) 145.1 (17) 141.3(12) 128.6 ( 1 4 ) 152.1 (13) 141.6 (12) 151.5 (15) 135.3 ( 1 2 ) 130. 6 (12) 139.6 (13) 136.5 (14) 137.…”

Section: -C(14)mentioning

confidence: 97%

Synthese und Strukturuntersuchung von Pyridin‐Borabenzol und Pyridin‐2‐Boranaphthalin

et al. 1985

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“…Although boratabenzene complexes of group 10 transition metals are known, very little research has been performed in the field since the first complexes were reported in the mid 1970`s by Herberich. [5][6][11][12][13] These reported complexes were variants of traditional 13 Our group has been actively experimenting with a Pt-Cl-B halide bridged borabenzene species noteworthy as it is the only example of this coordination mode for borabenzene transition metal species ever confirmed. 5,6 The addition of two equivalents of K + [DTBB]to NiBr2(PPh3)2 in THF afforded an immediate shift in color for the reaction crude from the green NiBr2(PPh3)2 solution to a reddishblack solution after 6 hours (Scheme 2).…”

Section: Synthesis Of the Metal Complexesmentioning

confidence: 99%

Coordination of a Di-tert-butylphosphidoboratabenzene Ligand to Electronically Unsaturated Group 10 Transition Metals

et al. 2012

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“…The procedures on product isolation were carried out in air. The starting compounds (η C 5 H 5 BMe)Rh(1,5 C 8 H 12 ) 15 and Tl[Tl(η 7,8 C 2 B 9 H 11 )] 16 were synthesized according to known procedures. 1 X ray diffraction study of complex 2.…”

Section: Methodsmentioning

confidence: 99%

Synthesis and structure of (boratabenzene)rhodacarborane (η-7,8-C2B9H11)Rh(η-C5H5BMe)

et al. 2010

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Derivate des Borabenzols, VIII: Ein neuer Weg zu Alkalimetallborinaten. Synthesen von Ruthenium‐, Osmium‐, Rhodium‐ und Platin‐Verbindungen mit Borinat‐Liganden

Cited by 52 publications

References 21 publications

Synthese und Strukturuntersuchung von Pyridin‐Borabenzol und Pyridin‐2‐Boranaphthalin

Synthese und Strukturuntersuchung von Pyridin‐Borabenzol und Pyridin‐2‐Boranaphthalin

Coordination of a Di-tert-butylphosphidoboratabenzene Ligand to Electronically Unsaturated Group 10 Transition Metals

Synthesis and structure of (boratabenzene)rhodacarborane (η-7,8-C2B9H11)Rh(η-C5H5BMe)

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