2008
DOI: 10.1002/ange.200801756
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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.

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Cited by 27 publications
(11 citation statements)
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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%
“…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%
“…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).…”
mentioning
confidence: 99%
“…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%