Komplexierung von 1,3‐Dihydro‐1,3‐diborapentafulven‐Derivaten mit Fe(CO)3‐Fragmenten: Synthesen, Kristall‐ und Elektronenstruktur von μ‐(η4:η5‐1,3‐Dihydro‐1,3‐diborapentafulven)‐bis (tricarbonyleisen)‐Komplexen

Feßenbecker, Achim; Enders, Markus; Pritzkow, Hans; Siebert, Walter; Hyla‐Kryspin, Isabella; Gleiter, Rolf

doi:10.1002/cber.19911240704

Cited by 15 publications

(6 citation statements)

References 12 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…The additional electron is supplied by the methylene group. Unlike the reported slipped triple-decker complexes with dihydro-diborafulvene ligands in the bridging position, [11,12] complexes 4a,b have an almost undistorted triple-decker structure (the projections of the Ru1 and Ru2 atoms on the C 3 B 2 plane are shifted from its centroid toward the B1 atom by only 0.208 and 0.146 Å for 4a and 0.208 and 0.120 Å for 4b, respectively).…”

Section: Dft Calculationsmentioning

confidence: 77%

“…The bonding in 1,3-dihydro-2-methylene-1,3-diborafulvene triple-decker complexes with two Fe(CO) 3 and the combination of Fe(CO) 3 /CoCp complex fragments [12] has been analyzed. These 32 VE compounds are diamagnetic because of their slip distortion, whereas non-distorted 32 VE triple-decker complexes are paramagnetic.…”

Section: Synthesis and Spectra Of The Complexes 2a 3a-c And 4bmentioning

confidence: 99%

“…According to DFT calculation compounds 4a and 4b hardly exhibit any slip distortion, whereas the known dinuclear complexes with µ-dihydrodiborafulvenes have slipped triple-decker structures. [11,12] …”

Section: Introductionmentioning

confidence: 98%

See 2 more Smart Citations

Paramagnetic (1,3‐Diborolyl)ruthenium Triple‐Decker Complexes and Transformation into Diamagnetic Complexes Having Bridging 1,3‐Diborafulvene Ligands

et al. 2010

Self Cite

View full text Add to dashboard Cite

The paramagnetic triple‐decker complexes [(Cp*Ru)2{μ‐(CMe)3(BCl)(BMe)}] (3b) and [(Cp*Ru)2{μ‐(CMe)3(BCl)2}] (3c) are formed by refluxing a mixture of [Cp*RuCl]4 and pentamethyl‐2,3‐dihydro‐1,3‐diborole in thf. In CH2Cl2 under air complex 3b slowly looses a hydrogen atom with formation of the diamagnetic triple‐decker [(Cp*Ru)2{μ‐η5:η6‐(CMe)3(BCl)(BCH2)}] (4b) with the unsymmetrical dihydrodiborafulvene derivative in a bridging position. The analogous complex [(Cp*Ru)2{μ‐η5:η6‐(CMe)3(BMe)‐(BCH2)}] (4a) is obtained by interaction of HCl with the triple‐decker [(Cp*Ru)2{μ‐(CMe)3(BMe)2}] (3a). According to calculations, complexes 4a and 4b have an almost non‐distorted triple‐decker arrangement with a strong bending of the B=CH2 group toward one of the Ru atoms. For the formation of 3b and 3c the chloro‐containing sandwich complexes [Cp*Ru{η5‐(CMe)3(BCl)(BR1)}] (2b,c; R1 = Me, Cl) are proposed as intermediates. The constitutions of the complexes are derived from NMR, MS and DFT data, and the molecular structure of 3b is confirmed by an X‐ray diffraction analysis.

show abstract

Section: Dft Calculationsmentioning

confidence: 77%

Section: Synthesis and Spectra Of The Complexes 2a 3a-c And 4bmentioning

confidence: 99%

See 1 more Smart Citation

Paramagnetic (1,3‐Diborolyl)ruthenium Triple‐Decker Complexes and Transformation into Diamagnetic Complexes Having Bridging 1,3‐Diborafulvene Ligands

et al. 2010

Self Cite

View full text Add to dashboard Cite

show abstract

“…Typische Beispiele sind die isomeren Verbindungen Benzo-1,3-dihydro-1,3-diborapentafulven (A) [1][2][3] und l,4-D ihydro-l,4-diboranaphthalin (B) [2,4,5]. Unsere Untersuchungen an 2,3-Dihydro-l,3-diborol (C) [6,7] und 1,4-Diboracyclohexen-2 (D) [8,9] haben gezeigt, daß auch partiell gesättigte O rganoborane in der K om plexchemie eingesetzt werden können.…”

unclassified

Neue Borkohlenstoffheterocyclen: Benzo-1,4-diboracyclohepten-2, 1,4-Diboracyclohepten-2 und das isomere 6.6-Dimethy 1-2-methyliden-1,3-diboracyclohexan / New Organoboran Heterocycles: Benzo-1,4-diboracycloheptene-2, 1,4-Diboracyclopentene-2 and the Isomeric 6,6-Dimethyl-2-methylidene-1,3-diboracyclohexane

Schulz

Seyffer

Deobald

et al. 1994

Zeitschrift Für Naturforschung B

View full text Add to dashboard Cite

2,3-B enzo-1,4-diboracycloheptene-2, 1,4-Diboracycloheptene-2, 6.6-Dim ethyl-2-m ethylidene-1,3-diboracyclohexane The reaction o f l,l-bis(trim ethylstannyl)-2-m ethylpropene-l and l,3-bis(dichloroboryl)-propane leads to the chloro derivate o f 6,6-dim ethyl-2-m ethylidene-l,3-diboracyclohexane (1 a), in which the Cl atom s are substituted by the dim ethylam ino and the methyl group to yield lb and lc . Similarly the benzo-l,4-diboracycloheptene-2 derivative 2 a is obtained from I,2-C6H4(SnM e3)2 and (C12B)2C3H6. Replacement o f the substituent leads to the dimethylami no (2b) and methyl derivatives (2c). R edox reaction between hexyne-3 and (I2B)2C3H 6 results in the formation o f l,4-diiodo-2,3-diethyl-l,4-diboracycloheptene-2 (3a), which is methylated to give 3c. The constitutions o f l a -c , 2 a~c and 3a,c are derived from N M R and MS data and are confirmed by X-ray structure analyses for 1 b and 2 b. Ungesättigte Organoborheterocyclen werden leicht durch geeignete M etallkomplexfragmente komplexiert. Typische Beispiele sind die isomeren Verbindungen Benzo-1,3-dihydro-1,3-diborapentafulven (A) [1-3] und l,4-D ihydro-l,4-diboranaphthalin (B) [2, 4, 5]. Unsere Untersuchungen an 2,3-Dihydro-l,3-diborol (C) [6, 7] und 1,4-Diboracyclohexen-2 (D) [8, 9] haben gezeigt, daß auch partiell gesättigte O rganoborane in der K om plexchemie eingesetzt werden können. Die wasser stofftragenden sp3-hybridisierten Kohlenstoffato me der Heterocyclen C und D werden während der Komplexierung dehydriert, wobei sie dann als 3-bzw. 4-Elektronendonoren wirken und rj5 bzw. rf an das Metallkomplexfragment gebunden sind. Die dehydrierende Komplexierung ist abhängig vom eingesetzten M etallkomplexfragment, wie die unterschiedliche Reaktivität von 2,3-Dihydro-l,3-diborol-Derivaten gegenüber (C5H 5)Ni-und (C5H 5)Co-Fragmenten zeigt. W ährend im ersten Fall eine dehydrierende Komplexierung stattfindet [10], bleibt der Komplexierung mit (C5H 5)CoTübingen 0 932-0 7 7 6 /9 4 /0 4 0 0 -0 4 6 5 /$ 01.00/0 einer C -H -B 3-Zentrenwechselwirkung [11] er halten.W ährend beim 2,3-Dihydro-l,3-diborol C und beim 1,4-Diboracyclohexen-2 D ein bzw. zwei sp3-hybridisierte Kohlenstoffatom e im Ring die Bor atom e trennen, befinden sich in den hier vorge stellten Heterocyclen drei C H 2-Gruppen zwischen den Boratom en. Komplexierungsversuche dieser O rganoborane sollen Inform ationen über die A k tivierung von C -H-Bindungen in diesen H etero cyclen liefern. W ir berichten hier zunächst über Synthese und Eigenschaften von 1,2 und 3.Cxjx 00 < > 0 Ergebnisse und DiskussionDarstellung und Eigenschaften von 1,2 und 3 Die zweifache Hydroborierung von Allen führt zu l,3-Bis(dichlorboryl)propan, dessen Lewis-acide BCl2-Funktionen mit Verbindungen des Typs R SnM e3 unter Knüpfung einer R -B -B indung und A bspaltung von M e3SnCl reagieren.

show abstract

“…This is shown by the form ation of metal complexes (1) M (CO)4 (M = Cr, M o) [1] and (1)Fe(CO)3 [2]; the latter react with a second Fe(CO)3 group to yield slipped triple-decker com plexes ( 1) [Fe(CO)3]2 [3], Form al replacement of a boryl group B -R 1 in 1 with the SiMe2 moiety should lead to the l-bora-3-silafulvene heterocycle (2). Our attem pts to synthesize 2 were not success ful.…”

mentioning

confidence: 99%

Notizen: Synthesis and Structure of a 2,4,5-Tris(methylene)-1-bora-3-silacyclopentane Derivative

Man

Pritzkow

Siebert

1991

Zeitschrift Für Naturforschung B

Self Cite

View full text Add to dashboard Cite

; the latter react with a second Fe(CO)3 group to yield slipped triple-decker com plexes ( 1) [Fe(CO)3]2 [3], Form al replacement of a boryl group B -R 1 in 1 with the SiMe2 moiety should lead to the l-bora-3-silafulvene heterocycle (2). Our attem pts to synthesize 2 were not success ful. However, a rearrangem ent of 4, analogous to that of the 2,4,5-tris(methylene)-l,3-diborolane (3) to yield 1 (R2 = C H (C H 3)2, R2 = C (C H 3) = C H 2) via a 1,5-hydrogen shift [4], may provide a route to 2. Here we report the synthesis and structure of the title com pound 4. ResultsSeveral unsaturated [5,6 ] and saturated [7] het erocyclic compounds with non-adjacent boron-silicon atoms are known. Recently, we described the unexpected formation o f a l,3-dibora-2,5-disilacyclohexane derivative by reacting com pound 5 with N a/K alloy [8]. 5 was obtained via hydroboration of Me3C -C = C -S iM e 2Cl with HBCl2 OEt2 and subsequent substitution of one chlorine atom by a N M e2 group. Treatm ent of 5 with 3,4-dilithio-2,5-dimethyl-2,4-hexadiene [9] in diethylether leads to 4 in 41% yield. The product can be dis tilled in vacuo and recrystallized from pentane at -2 0 °C.

show abstract

Komplexierung von 1,3‐Dihydro‐1,3‐diborapentafulven‐Derivaten mit Fe(CO)₃‐Fragmenten: Synthesen, Kristall‐ und Elektronenstruktur von μ‐(η⁴:η⁵‐1,3‐Dihydro‐1,3‐diborapentafulven)‐bis (tricarbonyleisen)‐Komplexen

Cited by 15 publications

References 12 publications

Paramagnetic (1,3‐Diborolyl)ruthenium Triple‐Decker Complexes and Transformation into Diamagnetic Complexes Having Bridging 1,3‐Diborafulvene Ligands

Paramagnetic (1,3‐Diborolyl)ruthenium Triple‐Decker Complexes and Transformation into Diamagnetic Complexes Having Bridging 1,3‐Diborafulvene Ligands

Notizen: Synthesis and Structure of a 2,4,5-Tris(methylene)-1-bora-3-silacyclopentane Derivative

Contact Info

Product

Resources

About