Thermischer Borylentransfer zur Synthese von Rhodium‐ und Iridiumborylenkomplexen

Braunschweig, Holger; Forster, Melanie; Kupfer, Thomas; Seeler, Fabian

doi:10.1002/ange.200801756

Cited by 27 publications

(11 citation statements)

References 44 publications

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“…The boron atom is situated approximately 1.402 Å (M′=Mo) and approximately 1.420 Å (M′=W) above the Rh1‐Rh2‐M′ plane in 3 and 4 , respectively. The average Rh−Rh bond length of 2.634 Å and Rh−B bond length of 2.04 Å resemble those observed in [Rh 4 {μ‐BN(SiMe 3 ) 2 } 2 (μ‐Cl) 4 (μ‐CO)(CO) 4 ] (Rh−Rh 2.5786(3) Å; Rh−B 2.003(3)–2.076(3) Å) and [{(η 5 ‐C 5 H 5 )(OC)Rh} 2 {μ‐BN‐(SiMe 3 ) 2 }] (Rh−Rh 2.668(3) Å; Rh−B 2.054(2) Å) . Similarly, the W1−B1 and Mo1−B1 bond lengths of 2.396(5) and 2.381(3) Å are comparable with the bridging borylene complexes [(Cp*Co) 2 (μ‐CO)(μ 3 ‐BH)W(CO) 5 ] (2.406(5) Å) and [(Cp*Co) 2 (μ‐CO)(μ 3 ‐BH)Mo(CO) 5 ] 2.406(5) Å, respectively.…”

Section: Resultssupporting

confidence: 68%

New Trinuclear Complexes of Group 6, 8, and 9 Metals with a Triply Bridging Borylene Ligand

Yuvaraj

Bhattacharyya

Prakash

et al. 2016

Chemistry A European J

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Trinuclear complexes of group 6, 8, and 9 transition metals with a (μ3 -BH) ligand [(μ3 -BH)(Cp*Rh)2 (μ-CO)M'(CO)5 ], 3 and 4 (3: M'=Mo; 4: M'=W) and 5-8, [(Cp*Ru)3 (μ3 -CO)2 (μ3 -BH)(μ3 -E)(μ-H){M'(CO)3 }] (5: M'=Cr, E=CO; 6: M'=Mo, E=CO; 7: M'=Mo, E=BH; 8: M'=W, E=CO), have been synthesized from the reaction between nido-[(Cp*M)2 B3 H7 ] (nido-1: M=Rh; nido-2: M=RuH, Cp*=η(5) -C5 Me5 ) and [M'(CO)5 ⋅thf] (M'=Mo and W). Compounds 3 and 4 are isoelectronic and isostructural with [(μ3 -BH)(Cp*Co)2 (μ-CO)M'(CO)5 ], (M'=Cr, Mo and W) and [(μ3 -BH)(Cp*Co)2 (μ-CO)(μ-H)2 M''H(CO)3 ], (M''=Mn and Re). All compounds are composed of a bridging borylene ligand (B-H) that is effectively stabilized by a trinuclear framework. In contrast, the reaction of nido-1 with [Cr(CO)5 ⋅thf] gave [(Cp*Rh)2 Cr(CO)3 (μ-CO)(μ3 -BH)(B2 H4 )] (9). The geometry of 9 can be viewed as a condensed polyhedron composed of [Rh2 Cr(μ3 -BH)] and [Rh2 CrB2 ], a tetrahedral and a square pyramidal geometry, respectively. The bonding of 9 can be considered by using the polyhedral fusion formalism of Mingos. All compounds have been characterized by using different spectroscopic studies and the molecular structures were determined by using single-crystal X-ray diffraction analysis.

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Section: Resultssupporting

confidence: 68%

New Trinuclear Complexes of Group 6, 8, and 9 Metals with a Triply Bridging Borylene Ligand

Yuvaraj

Bhattacharyya

Prakash

et al. 2016

Chemistry A European J

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“…The [15] can be generated in a straightforward reaction under mild thermal conditions by borylene exchange between [(OC) 5 Mo=BN(SiMe 3 ) 2 ] (2) [11b] and 1 (Scheme 1).…”

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confidence: 99%

Towards Homoleptic Borylene Complexes: Incorporation of Two Borylene Ligands into a Mononuclear Iridium Species

et al. 2010

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The incorporation of subvalent Group 13 ligands into the coordination sphere of transition metals has always been a challenging task, particularly in the formation of homoleptic complexes. Although metastable or sterically protected subvalent E I (E = Al, Ga, In) precursors have become accessible during the last few decades, [1] for example, E I halides, [1, 2] [{Cp*E} n ] (Cp* = h 5 -C 5 Me 5 ), [1, 3] and [{EC(SiMe 3 ) 3 } n ], [1, 4] stable and isolable boron congeners have still not been prepared. For this reason, only homoleptic transition-metal complexes with Al-, Ga-, and In-based ligands have so far been realized, for example, mononuclear [Ni(ECp*) 4 ] (A; E = Al, Ga) [5,6] and [Ni{EC(SiMe 3 ) 3 } 4 ] (B; E = Ga, In), [7,8] as well as numerous heteroleptic examples with two or more E I ligands. [9] The corresponding subvalent boron ligands, that is, borylenes, have only been generated directly in the coordination sphere of transition metals [10] to form species such as [(OC) 5 M=BN(SiMe 3 ) 2 ] (C; M = Cr, Mo, W).[11] To date, both mononuclear borylene complexes containing more than one borylene substituent as well as homoleptic borylene species have continuously resisted isolation. Nonetheless, borylene complexes have sparked increasing interest in fundamental organometallic research because of their close relationship with important organometallic compounds such as carbene, carbyne, and vinylidene complexes, and the similarity of the bonding properties of borylene and carbonyl ligands. Numerous experimental and computational studies have previously examined these bonding properties in detail.[10] It was thus shown that BR has stronger s-donor and p-acceptor properties than CO, which makes the M À BR bond even more stable with respect to homolytic dissociation than the M À CO bond, but in turn it is kinetically labile due to the high polarity. Getting back to the series of related ligands mentioned above, the predominance of the CO and carbene ligands in organometallic chemistry is also manifested by the fact that homoleptic complexes have only been accessible with these two ligands. By contrast, the incorporation of two borylene or carbyne ligands into a mononuclear transition-metal complex has always proven problematic. While in the former case a suitable synthetic approach is still lacking, [12] the synthesis of bis(carbyne) species is further hampered by reductive coupling to form acetylenes, particularly with alkyl-substituted carbynes.[13] It has not yet been elucidated whether bis-(borylene) complexes are resistant towards reductive coupling. In any case, it would require the availability of experimental data before this question could be clarified. We have been studying borylene complexes for more than a decade now, but all our efforts to synthesize a complex with more than one terminal borylene have so far failed.Herein, we describe the successful generation and isolation of a long-sought after mononuclear, terminal bis-(borylene) complex derived from the [Cp*Ir] half-sandwich fragment,...

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“…The cation has overall non‐crystallographic C 2 v symmetry. The Rh–B distances [2.015(6) and 1.983(7) Å] are shorter than those in the related bridging aminoborylene complex [{Rh(η 5 ‐C 5 H 5 )(CO)} 2 {µ‐BN(SiMe 3 ) 2 }] [2.054(2) Å] and aminoborane complex [{Rh(P i Pr 2 (CH 2 ) 3 P i Pr 2 )} 2 (µ‐H)(µ‐BH 2 NH 2 )][BAr F 4 ] [ I , 2.055(5), 2.070(5) Å] but fall within the range seen for monomeric rhodium aminoboryl complexes of 2.034–1.929 Å , , . The B–N distance in 7 [1.379(8) Å] is comparable to that measured in bridging aminoborylenes, for example [{Rh(η 5 ‐C 5 H 5 )(CO)} 2 {µ‐BN(SiMe 3 ) 2 }] [1.399(6) Å], and the only structurally characterised µ‐BNMe 2 example [{Mn(η 5 ‐C 5 H 5 )(CO) 2 } 2 (µ‐BNMe 2 )] [1.39(1) Å] …”

Section: Resultsmentioning

confidence: 99%

“…I , δ ( 11 B) 51.1] . However, the sharp signals observed for the hydrides in the 1 H NMR spectrum, that are unaffected by 11 B coupling, point to a bridging dihydrido amino borylene motif, which would be expected to show lower field chemical shifts in the 11 B NMR spectra (>90 ppm),, although examples have been observed as far upfield as 74 ppm . An obvious geometric distinction between a bridging aminoborane (µ‐H 2 BNR 2 ) and a bridging aminoborylene dihydride (µ‐BNR 2 ) structure is the orientation of the NR 2 moiety with respect to the RhBRh plane, as depicted in Figure .…”

Section: Resultsmentioning

confidence: 99%

Fluoroarene Complexes with Small Bite Angle Bisphosphines: Routes to Amine–Borane and Aminoborylene Complexes

et al. 2017

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Thermischer Borylentransfer zur Synthese von Rhodium‐ und Iridiumborylenkomplexen

Abstract: Bei Raumtemperatur liefert der Borylentransfer von [(OC)5MoBN(SiMe3)2] auf [(η5‐C5R5)M(CO)2] (M=Rh, R=H; M=Ir, R=Me) terminale Borylenkomplexe von Rhodium und Iridium (siehe Schema). Der Iridiumkomplex 1 konnte röntgenstrukturanalytisch charakterisiert werden.

Cited by 27 publications

References 44 publications

New Trinuclear Complexes of Group 6, 8, and 9 Metals with a Triply Bridging Borylene Ligand

New Trinuclear Complexes of Group 6, 8, and 9 Metals with a Triply Bridging Borylene Ligand

Towards Homoleptic Borylene Complexes: Incorporation of Two Borylene Ligands into a Mononuclear Iridium Species

Fluoroarene Complexes with Small Bite Angle Bisphosphines: Routes to Amine–Borane and Aminoborylene Complexes

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