Heterometalation of 1,1′-Bis(<i>ortho</i>-carborane)

Chan, Antony P. Y.; Rosair, Georgina M.; Welch, Alan J.

doi:10.1021/acs.inorgchem.8b01166

Cited by 14 publications

(13 citation statements)

References 34 publications

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“…(Scheme 1, c) products [9]. Notably, an example of stepwise deboronation/metalation-deboronation/heterometalation is also reported [11]. Here we document an expansion of the bimetallic metallacarboranes library via the double deboronation/nickelation of 1,1′-bis(o-carborane).…”

Section: Introductionsupporting

confidence: 56%

“…The formation of intramolecular dihydrogen bonding associated with CH atoms of one cage and BH atoms of the other cage results from the relatively protonic and hydridic nature of the CH and BH atoms, respectively. 11 B NMR analysis of individual vertices for 3,1,2-MC 2 B 9 compounds established that the most hydridic BH atoms are H5 and H6 [18]. In the case of rac-3, the orientation of two {(dppe)NiC 2 B 9 } cages enables two sets of intramolecular dihydrogen bonds, CH2• • • BH6 i 2.07(3) Å (where i = 1 − x, y, 0.5 − z) and its symmetry equivalent, CH2 i • • • BH6.…”

Section: Dihydrogen Interaction In 3 and Isomerisation In 4αmentioning

confidence: 99%

“…Variation in the isomer type with cobalt has been achieved by varying the metalation source, forming either 3,1,2-CoC 2 B 9 -3 ,1 ,2 -CoC 2 B 9 (non-isomerised) or 3,1,2-CoC 2 B 9 -2 ,1 ,8 -CoC 2 B 9 (isomerised) (Scheme 1, c) products [9]. Notably, an example of stepwise deboronation/metalationdeboronation/heterometalation is also reported [11]. Here we document an expansion of the bimetallic metallacarboranes library via the double deboronation/nickelation of 1,1 -bis(o-carborane).…”

Section: Introductionmentioning

confidence: 99%

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Exploration of Bis(nickelation) of 1,1′-Bis(o-carborane)

Mandal

Rosair

2020

Crystals

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The metalation of [Tl]2[1-(1′-3′,1′,2′-closo-TlC2B9H10)-3,1,2-closo-TlC2B9H10], with the smaller {Ni(dmpe)} fragment sourced from [Ni(dmpe)Cl2], is explored. The bis(metalated) products are obtained as a diastereoisomeric mixture. These isomers were separated, fully characterised spectroscopically and crystallographically and identified as rac-[1-(1′-3′-(dmpe)-3′,1′,2′-closo-NiC2B9H10)-3-(dmpe)-3,1,2-closo-NiC2B9H10] (1) and meso-[1-(1′-3′-(dmpe)-3′,1′,2′-closo-NiC2B9H10)-3-(dmpe)-3,1,2-closo-NiC2B9H10] (2). Previously, these 3,1,2-NiC2B9-3′,1′,2′-NiC2B9 architectures (where both cages are not isomerised), were inaccessible, and thus new structures can be achieved during bis(nickelation) with {Ni(dmpe)}. Further, the metalation of the tetra-thallium salt with the bulky {Ni(dppe)} fragment sourced from [Ni(dppe)Cl2] was also studied. These bis(nickelated) products were also fully characterised and are afforded as the stereospecific species rac-[1-(1′-3′-(dppe)-3′,1′,2′-closo-NiC2B9H10)-3-(dppe)-3,1,2-closo-NiC2B9H10] (3) and [1-(2′-4′-(dppe)-4′,1′,2′-closo-NiC2B9H10)-3-(dppe)-3,1,2-closo-NiC2B9H10] (4α). In the latter metalation, compound 3 shows intramolecular dihydrogen bonding, contributing to the stereospecificity, whereas isomerisation from 3,1,2 to 4,1,2- in the 4α is related to steric relief.

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Section: Introductionsupporting

confidence: 56%

Section: Dihydrogen Interaction In 3 and Isomerisation In 4αmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Exploration of Bis(nickelation) of 1,1′-Bis(o-carborane)

Mandal

Rosair

2020

Crystals

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“…Recent years have witnessed a significant amount of interest in the chemistry of bis(carboranes) [1][2][3][4], particularly 1,1 -bis(ortho-carborane), formally [1-(1 -closo-1 ,2 -C 2 B 10 H 11 )-closo-1,2-C 2 B 10 H 11 ] (I), Scheme 1. This species offers a versatile scaffold for derivatisation and, amongst other studies, we have reported the single deboronation/metalation [5], double deboronation/homometalation [6] and stepwise deboronation/metalation-deboronation/heterometalation [7] of I, the latter including the use of {Rh(H)(PPh 3 ) 2 } fragments to afford homogeneous catalyst precursors [8].…”

Section: Introductionmentioning

confidence: 81%

“…HNMe 3 ][8-(7 -nido-7 ,8 -C 2 B 19 H 11 )-2-(p-cymene)-closo-2,1,8-RuC 2 B 9 H 10 ] ([HNMe 3 ]III Ru ) [7], [HNMe 3 ][8-(7 -nido-7 ,8 -C 2 B 19 H 11 )-2-Cp-closo-2,1,8-CoC 2 B 9 H 10 ] ([HNMe 3 ]III CoCp )[7] and [Rh(PPh 3 )3 Cl][16] were prepared according to the literature. All other reagents were purchased from Sigma Aldrich Ltd. (Gillingham, UK) or Alfa Aesar (Heysham, UK) and used without further purification.…”

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confidence: 99%

Exopolyhedral Ligand Orientation Controls Diastereoisomer in Mixed-Metal Bis(Carboranes)

2020

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Heterobimetallic derivatives of a bis(carborane), [µ 7,8 -(1 ,3 −3 -Cl-3 -PPh 3 -closo-3 ,1 ,2 -RhC 2 B 9 H 10 )-2-(p-cymene)-closo-2,1,8-RuC 2 B 9 H 10 ] (1) and [µ 7,8 -(1 ,3 −3 -Cl-3 -PPh 3 -closo-3 ,1 ,2 -RhC 2 B 9 H 10 )-2-Cp-closo-2,1,8-CoC 2 B 9 H 10 ] (2) have been synthesised and characterised, including crystallographic studies. A minor co-product during the synthesis of compound 2 is the new species [8-{8 -2 -H-2 ,2 -(PPh 3 ) 2 -closo-2 ,1 ,8 -RhC 2 B 9 H 10 }-2-Cp-closo-2,1,8-CoC 2 B 9 H 10 ] (3), isolated as a mixture of diastereoisomers. Although, in principle, compounds 1 and 2 could also exist as two diastereoisomers, only one (the same in both cases) is formed. It is suggested that the preferred exopolyhedral ligand orientation in the rhodacarboranes in the non-observed diastereoisomers would lead to unacceptable steric crowding between the PPh 3 ligand and either the p-cymene (compound 1) or Cp (compound 2) ligand of the ruthenacarborane or cobaltacarborane, respectively.

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Selective Functionalization of BH Bond of o ‐Carboranes

Cao¹,

Zhang²,

Wu³

et al. 2022

Handbook of CH-Functionalization

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Icosahedral carboranes are a class of carbon–boron molecular clusters with three‐dimensional aromaticity, which have growing applications in functional materials, boron neutron capture therapy agents, organometallic, and coordination chemistry. To further expand the application of o ‐carboranes, the functionalization of o ‐carboranes with diverse groups and controllable regioselectivity has been a challenging subject as the 10 BH bonds are not fully equal and have a slight difference in reactivity. In the past six years, transition metal‐catalyzed BH activation has been proved to be a powerful tool to accomplish the regioselective functionalization of o ‐carboranes and achieved much advancement in this field. This article summarizes recent advances around BH activation.

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Heterometalation of 1,1′-Bis(ortho-carborane)

Cited by 14 publications

References 34 publications

Exploration of Bis(nickelation) of 1,1′-Bis(o-carborane)

Exploration of Bis(nickelation) of 1,1′-Bis(o-carborane)

Exopolyhedral Ligand Orientation Controls Diastereoisomer in Mixed-Metal Bis(Carboranes)

Selective Functionalization of BH Bond of o ‐Carboranes

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