TY - JOUR
T1 - Metalation of Bis(meta-carborane)
AU - Jeans, Rebekah J.
AU - Chan, Antony P. Y.
AU - Murrell, Ashton H.
AU - Chouman, Heather A.
AU - Rosair, Georgina M.
AU - Welch, Alan J.
N1 - Funding Information:
We thank the Engineering & Physical Sciences Research Council and the CRITICAT Centre for Doctoral Training for PhD studentships awarded to R.J.J. and A.P.Y.C. (grant no. EP/L016419/1).
Publisher Copyright:
© 2021 Elsevier B.V.
PY - 2021/10/1
Y1 - 2021/10/1
N2 - The first metallacarborane derivatives of 1,1′-bis(meta-carborane), specifically [1-(1′-closo-1′,7′-C2B10H11)-2-(p-cymene)-closo-2,1,7-RuC2B9H10] (2), [1-(1′-closo-1′,7′-C2B10H11)-2-(p-cymene)-6-OEt-closo-2,1,7-RuC2B9H9] (3), [1-(1′-closo-1′,7′-C2B10H11)-2-(C6Me6)-closo-2,1,7-RuC2B9H10] (4), [1-(1′-closo-1′,7′-C2B10H11)-2-(C6Me6)-6-OEt-closo-2,1,7-RuC2B9H9] (5), [1-(1′-closo-1′,7′-C2B10H11)-2-Cp-closo-2,1,7-CoC2B9H10] (6) and [1-(1′-closo-1′,7′-C2B10H11)-2-Cp*-closo-2,1,7-CoC2B9H10] (7), have been prepared by deboronation of one cage and subrogation of the {BH} fragment removed by an isolobal {Ru(arene)}, {CoCp} or {CoCp*} fragment. In the case of the {Ru(arene)} species, attack on the products 2 and 4 by EtO− resulted in derivatives 3 and 5, respectively, in which an OEt group is attached to B6 of the metallacarborane cage. All products were characterised by multinuclear NMR spectroscopy and single-crystal X-ray diffraction. All are of the form the 2,1,7-MC2B9-1′,7′-C2B10, and even though the structural studies reveal clear evidence of steric crowding between the arene or Cp/Cp* ligand on the metal and the pendant carborane cage, no isomerisation of the metallacarborane to either 2,1,8-MC2B9 or 2,1,12-MC2B9 occurs, even on heating to reflux in toluene.
AB - The first metallacarborane derivatives of 1,1′-bis(meta-carborane), specifically [1-(1′-closo-1′,7′-C2B10H11)-2-(p-cymene)-closo-2,1,7-RuC2B9H10] (2), [1-(1′-closo-1′,7′-C2B10H11)-2-(p-cymene)-6-OEt-closo-2,1,7-RuC2B9H9] (3), [1-(1′-closo-1′,7′-C2B10H11)-2-(C6Me6)-closo-2,1,7-RuC2B9H10] (4), [1-(1′-closo-1′,7′-C2B10H11)-2-(C6Me6)-6-OEt-closo-2,1,7-RuC2B9H9] (5), [1-(1′-closo-1′,7′-C2B10H11)-2-Cp-closo-2,1,7-CoC2B9H10] (6) and [1-(1′-closo-1′,7′-C2B10H11)-2-Cp*-closo-2,1,7-CoC2B9H10] (7), have been prepared by deboronation of one cage and subrogation of the {BH} fragment removed by an isolobal {Ru(arene)}, {CoCp} or {CoCp*} fragment. In the case of the {Ru(arene)} species, attack on the products 2 and 4 by EtO− resulted in derivatives 3 and 5, respectively, in which an OEt group is attached to B6 of the metallacarborane cage. All products were characterised by multinuclear NMR spectroscopy and single-crystal X-ray diffraction. All are of the form the 2,1,7-MC2B9-1′,7′-C2B10, and even though the structural studies reveal clear evidence of steric crowding between the arene or Cp/Cp* ligand on the metal and the pendant carborane cage, no isomerisation of the metallacarborane to either 2,1,8-MC2B9 or 2,1,12-MC2B9 occurs, even on heating to reflux in toluene.
KW - Cobalt
KW - Crystal structure
KW - Metallacarborane
KW - NMR spectroscopy
KW - Ruthenium
KW - Synthesis
UR - http://www.scopus.com/inward/record.url?scp=85111334453&partnerID=8YFLogxK
U2 - 10.1016/j.jorganchem.2021.121980
DO - 10.1016/j.jorganchem.2021.121980
M3 - Article
AN - SCOPUS:85111334453
SN - 0022-328X
VL - 950
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
M1 - 121980
ER -