Synthesis and Structure of Amido‐ and Imido(pentafluorophenyl)borane Zirconocene and Hafnocene Complexes: NH and BH Activation

Jacobs, Elizabeth A.; Fuller, Anna; Coles, Simon J.; Jones, G.; Tizzard, Graham J.; Wright, Joseph A.; Lancaster, Simon

doi:10.1002/chem.201200704

Cited by 16 publications

(16 citation statements)

References 62 publications

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“…Complex 6 , an analogue of 3 , is formally the product of oxidative addition of the NH bond of ammonia–borane to zirconocene. Very recently, a B‐disubstituted analogue of 6 , complex [Cp 2 Zr(H){NH 2 B(C 6 F 5 ) 2 H}] ( 7 ), has been reported by Lancaster and co‐workers 11g. Interestingly, Wolstenholme, McGrady, and co‐workers have isolated a paramagnetic Ti III amidoborane complex ( 8 ) from the reaction of [Cp 2 TiCl 2 ] with Li[NH 2 BH 3 ] (2 equiv) 13.…”

Section: Methodsmentioning

confidence: 99%

Paramagnetic Titanium(III) and Zirconium(III) Metallocene Complexes as Precatalysts for the Dehydrocoupling/Dehydrogenation of Amine–Boranes

Helten¹,

Dutta²,

Vance³

et al. 2012

Angew Chem Int Ed

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Complexes of Group 4 metallocenes in the +3 oxidation state and amidoborane or phosphidoborane function as efficient precatalysts for the dehydrocoupling/dehydrogenation of amine-boranes, such as Me(2) NH⋅BH(3). Such Ti(III) -amidoborane complexes are generated in [Cp(2)Ti]-catalyzed amine-borane dehydrocoupling reactions, for which diamagnetic M(II) and M(IV) species have been previously postulated as precatalysts and intermediates.

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Section: Methodsmentioning

confidence: 99%

Paramagnetic Titanium(III) and Zirconium(III) Metallocene Complexes as Precatalysts for the Dehydrocoupling/Dehydrogenation of Amine–Boranes

Helten¹,

Dutta²,

Vance³

et al. 2012

Angew Chem Int Ed

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“…86 NaNMe 2 BH 3 has also 88 Lancaster and co-workers have studied the effect of electronwithdrawing substituents at boron on the reactivity of lithium amidoboranes. [89][90][91] To this end, the compounds LiNH 2 -B(C 6 F 5 ) n (H) 3Àn (n = 1-3) were prepared as THF solvates, by reaction of the appropriate ammonia-borane precursor with n-butyllithium or LiN(SiMe 3 ) 2 . 91 Addition of [12]crown-4 to LiNH 2 B(C 6 F 5 ) 2 HÁ(THF) 2 (7ÁTHF 2 ) produced the crown ether adduct ( [12]crown-4)LiNH 2 B(C 6 F 5 ) 2 H, which could be structurally characterised by X-ray diffraction.…”

Section: Group 1 Mnr 2 Bh 3 Compounds As Reagents In Salt Metathesis mentioning

confidence: 99%

“…[89][90][91] To this end, the compounds LiNH 2 -B(C 6 F 5 ) n (H) 3Àn (n = 1-3) were prepared as THF solvates, by reaction of the appropriate ammonia-borane precursor with n-butyllithium or LiN(SiMe 3 ) 2 . 91 Addition of [12]crown-4 to LiNH 2 B(C 6 F 5 ) 2 HÁ(THF) 2 (7ÁTHF 2 ) produced the crown ether adduct ( [12]crown-4)LiNH 2 B(C 6 F 5 ) 2 H, which could be structurally characterised by X-ray diffraction. At 1.544(2) Å, the B-N bond is markedly shorter than in the parent amine-borane, NH 3 B(C 6 F 5 ) 2 H (1.6034(19) Å), but unremarkable compared to other amidoborane species.…”

Section: Group 1 Mnr 2 Bh 3 Compounds As Reagents In Salt Metathesis mentioning

confidence: 99%

s-Block amidoboranes: syntheses, structures, reactivity and applications

Stennett

Harder

2016

Chem. Soc. Rev.

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Metal amidoborane compounds of the alkali- and alkaline earth metals have in recent years found applications in diverse disciplines, notably as hydrogen storage materials, as reagents for the reduction of organic functional groups and as catalysts and intermediates in dehydrocoupling reactions. These functions are connected by the organometallic chemistry of the MNR2BH3 group. This review focusses on central aspects of the s-block amidoborane compounds - their syntheses, structures and reactivity. Well-defined amidoborane complexes of group 2 metals are now available by a variety of solution-phase routes, which has allowed a more detailed analysis of this functional group, which was previously largely confined to solid-state materials chemistry. Structures obtained from X-ray crystallography have begun to provide increased understanding of the fundamental steps of key processes, including amine-borane dehydrocoupling and hydrogen release from primary and secondary amidoboranes. We review structural parameters and reactivity to rationalise the effects of the metal, nitrogen substituents and supporting ligands on catalytic performance and dehydrogenative decomposition routes. Mechanistic features of key processes involving amidoborane compounds as starting materials or intermediates are discussed, alongside emerging applications such as the use of group 1 metal amidoboranes in synthesis. Finally, the future prospects of this vibrant branch of main group chemistry are evaluated.

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“…A search of the Cambridge Structural Database (Version 5.37, update February 2017; Groom et al, 2016) for DMAP-borane adducts yielded only two structures: VOGJEI (Chu, et al, 2014) and JUDQAA (Lesley et al, 1998). A search for phenylbased monoorganoborane-amine adducts (Ph-BH 2 -NR 3 ) yielded four structures: UTOZEJ (Hubner et al, 2012), BEXQOM (Mé nard & Stephan, 2013), EPOYAK (Franz et al, 2011), and GEBNAE (Jacobs et al, 2012). In all four of these structures, the B-N bonds are approximately perpendicular to the plane of the arene rings.…”

Section: Database Surveymentioning

confidence: 99%

Crystal structure and Hirshfield analysis of the 4-(dimethylamino)pyridine adduct of 4-methoxyphenylborane

Shooter¹,

Allen²,

Tinsley³

et al. 2017

Acta Cryst E

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The title compound [systematic name: 4-(dimethylamino)pyridine–4-methoxyphenylborane (1/1)], C14H19BN2O, contains two independent molecules in the asymmetric unit. Both molecules exhibit coplanar, mostlysp2-hybridized methoxy and dimethylamino substituents on their respective aromatic rings, consistent with π-donation into the aromatic systems. The B—H groups exhibit an intramolecular close contact with a C—H group of the pyridine ring, which may be evidence of electrostatic attraction between the hydridic B—H and the electropositive aromatic C—H. There appears to be weak C—H...π(arene) interactions between two of the H atoms of an aminomethyl group and the methoxy-substituted benzene ring of the other independent molecule, and another C—H...π (arene) interaction between one of the pyridine ring H atoms and the same benzene ring.

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Synthesis and Structure of Amido‐ and Imido(pentafluorophenyl)borane Zirconocene and Hafnocene Complexes: NH and BH Activation

Cited by 16 publications

References 62 publications

Paramagnetic Titanium(III) and Zirconium(III) Metallocene Complexes as Precatalysts for the Dehydrocoupling/Dehydrogenation of Amine–Boranes

Paramagnetic Titanium(III) and Zirconium(III) Metallocene Complexes as Precatalysts for the Dehydrocoupling/Dehydrogenation of Amine–Boranes

s-Block amidoboranes: syntheses, structures, reactivity and applications

Crystal structure and Hirshfield analysis of the 4-(dimethylamino)pyridine adduct of 4-methoxyphenylborane

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