From alkaline earth to coinage metal carboranyls

Michael Hill; Kyle Pearce; Louis Morris; Thomas Robinson; Andrew Johnson; Mary Mahon

doi:10.1039/D4DT00478G

From alkaline earth to coinage metal carboranyls

Michael Hill, Kyle Pearce, Louis Morris, Thomas Robinson, Andrew Johnson, Mary Mahon

Research output: Contribution to journal › Article › peer-review

2 Citations (SciVal)

Abstract

The β-diketiminato calcium and magnesium complexes, [(BDI)MgnBu] and [(BDI)CaH]2 (BDI = HC{C(Me)NDipp}2; Dipp = 2,6-di-isopropylphenyl), react with ortho-carborane (o-C2B10H12¬) to provide the respective [(BDI)Ae(o-C2B10H11)] (Ae = Mg or Ca) complexes. While the lighter group 2 species is a monomer with magnesium in a distorted trigonal planar environment, the heavier analogue displays a puckered geometry at calcium in the solid state due to Ca‧‧‧H-B intermolecular interactions. These secondary contacts are, however, readily disrupted upon addition of THF to provide the 4-coordinate monomer, [(BDI)Ca(THF)(o-C2B10H11)]. [(BDI)Mg(o-C2B10H11)] was reacted with NHCIPrMCl (NHCIPr = 1,3-bis(isopropyl)imidazol-2-ylidene; M = Cu, Ag, Au) to provide NHCIPrM(o-C2B10H11), rare C-bonded examples of coinage metal derivatives of unsubstituted (o-C2B10H11) and confirming the alkaline earth compounds as viable reagents for the transmetalation of the carboranyl anion.

Original language	English
Pages (from-to)	6653-6659
Number of pages	7
Journal	Dalton Transactions
Volume	53
Issue number	15
Early online date	20 Mar 2024
DOIs	https://doi.org/10.1039/D4DT00478G
Publication status	Published - 21 Apr 2024

Data Availability Statement

See ESI for complete synthetic, and crystallographic details. CCDC codes 2332977–2332982 contain the supplementary crystallographic data for this paper.

Funding

We thank the EPSRC (EP/X01181X/1) for support of this research.

Access to Document

10.1039/D4DT00478GLicence: CC BY

Cite this

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title = "From alkaline earth to coinage metal carboranyls",

abstract = "The β-diketiminato calcium and magnesium complexes, [(BDI)MgnBu] and [(BDI)CaH]2 (BDI = HC{C(Me)NDipp}2; Dipp = 2,6-di-isopropylphenyl), react with ortho-carborane (o-C2B10H12¬) to provide the respective [(BDI)Ae(o-C2B10H11)] (Ae = Mg or Ca) complexes. While the lighter group 2 species is a monomer with magnesium in a distorted trigonal planar environment, the heavier analogue displays a puckered geometry at calcium in the solid state due to Ca‧‧‧H-B intermolecular interactions. These secondary contacts are, however, readily disrupted upon addition of THF to provide the 4-coordinate monomer, [(BDI)Ca(THF)(o-C2B10H11)]. [(BDI)Mg(o-C2B10H11)] was reacted with NHCIPrMCl (NHCIPr = 1,3-bis(isopropyl)imidazol-2-ylidene; M = Cu, Ag, Au) to provide NHCIPrM(o-C2B10H11), rare C-bonded examples of coinage metal derivatives of unsubstituted (o-C2B10H11) and confirming the alkaline earth compounds as viable reagents for the transmetalation of the carboranyl anion.",

author = "Michael Hill and Kyle Pearce and Louis Morris and Thomas Robinson and Andrew Johnson and Mary Mahon",

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AU - Hill, Michael

AU - Pearce, Kyle

AU - Morris, Louis

AU - Robinson, Thomas

AU - Johnson, Andrew

AU - Mahon, Mary

PY - 2024/4/21

Y1 - 2024/4/21

N2 - The β-diketiminato calcium and magnesium complexes, [(BDI)MgnBu] and [(BDI)CaH]2 (BDI = HC{C(Me)NDipp}2; Dipp = 2,6-di-isopropylphenyl), react with ortho-carborane (o-C2B10H12¬) to provide the respective [(BDI)Ae(o-C2B10H11)] (Ae = Mg or Ca) complexes. While the lighter group 2 species is a monomer with magnesium in a distorted trigonal planar environment, the heavier analogue displays a puckered geometry at calcium in the solid state due to Ca‧‧‧H-B intermolecular interactions. These secondary contacts are, however, readily disrupted upon addition of THF to provide the 4-coordinate monomer, [(BDI)Ca(THF)(o-C2B10H11)]. [(BDI)Mg(o-C2B10H11)] was reacted with NHCIPrMCl (NHCIPr = 1,3-bis(isopropyl)imidazol-2-ylidene; M = Cu, Ag, Au) to provide NHCIPrM(o-C2B10H11), rare C-bonded examples of coinage metal derivatives of unsubstituted (o-C2B10H11) and confirming the alkaline earth compounds as viable reagents for the transmetalation of the carboranyl anion.

AB - The β-diketiminato calcium and magnesium complexes, [(BDI)MgnBu] and [(BDI)CaH]2 (BDI = HC{C(Me)NDipp}2; Dipp = 2,6-di-isopropylphenyl), react with ortho-carborane (o-C2B10H12¬) to provide the respective [(BDI)Ae(o-C2B10H11)] (Ae = Mg or Ca) complexes. While the lighter group 2 species is a monomer with magnesium in a distorted trigonal planar environment, the heavier analogue displays a puckered geometry at calcium in the solid state due to Ca‧‧‧H-B intermolecular interactions. These secondary contacts are, however, readily disrupted upon addition of THF to provide the 4-coordinate monomer, [(BDI)Ca(THF)(o-C2B10H11)]. [(BDI)Mg(o-C2B10H11)] was reacted with NHCIPrMCl (NHCIPr = 1,3-bis(isopropyl)imidazol-2-ylidene; M = Cu, Ag, Au) to provide NHCIPrM(o-C2B10H11), rare C-bonded examples of coinage metal derivatives of unsubstituted (o-C2B10H11) and confirming the alkaline earth compounds as viable reagents for the transmetalation of the carboranyl anion.

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From alkaline earth to coinage metal carboranyls

Abstract

Data Availability Statement

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Molecular s-block Assemblies for Redox-active Bond Activation and Catalysis: Repurposing the s-block as 3d-elements

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From alkaline earth to coinage metal carboranyls

Abstract

Data Availability Statement

Funding

Access to Document

Other files and links

Fingerprint

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Molecular s-block Assemblies for Redox-active Bond Activation and Catalysis: Repurposing the s-block as 3d-elements

Cite this