Photolytic carbonyl insertion and solvolysis of 6-[(η5-C5H5)Fe(CO)2]B10H13

Metallaheteroborane chemistry: Part 16. Contrasting metal to heteroborane bonding modes in isoelectronic {MC2B9} and {MAs2B9} clusters. Synthesis and characterisation of [9-{Fe(CO)2(η5-C5H5)}-nido-7,8-C2B9H12], [7-{Fe(CO)2(η5-C5H5)}-nido-7,8-As2B9H10] and [7-{M(CO)2(η7-C7H7<

“…It is well known that the {Fe(CO) 2 -(η 5 -C 5 H 5 )} radical is a common initial photogenerated product from {Fe(CO) 2 (η 5 -C 5 H 5 )}-containing species and that THF is a radical-supporting solvent which sometimes becomes involved in the radical reactions. An example of this is observed in the photolysis of [6- 41 In this general area, a reaction that is perhaps more similar to the conversion of 43 Two products are isolatable in approximately equal amounts: viz. diamagnetic orange [1-(η 5 -C 5 H 5 )-1-(H)-closo-1,2,3-FeC 2 B 4 H 6 ], 24, which from 1 H NMR spectroscopic evidence contains an Fe-H bond, and brown paramagnetic [1-(η 5 -C 5 H 5 )-closo-1,2,3-FeC 2 B 4 H 6 ], 25.…”

Synthesis of the First hyper-closo-Type Monocarbon Ruthenacarboranes by Polyhedral Contraction of [nido-B10H12CH]- and Molecular Structure of 2-Cl-2,5-(Ph3P)2-2-H-3,9-(MeO)2-2,1-RuCB8H6

“…The [ nido- B 10 H 12 CH] - anion ( 1 ) is normally used as a convenient source for the π-monocarbollide ligand, which, in turn, is most widely employed for the preparation of 12-vertex monocarbon closo -metallacarboranes via treatment with transition-metal reagents . In this paper we demonstrate an unprecedented use of 1 as a precursor to smaller cage monocarbon carborane ligands, and, in particular, we report the first example of a polyhedral contraction reaction of 1 where the elimination of 2 and even 4 boron-containing fragments is effected by the action of 16-electron RuCl 2 (PPh 3 ) 3 ( 2 ).…”

Acyl chloride carbon insertion into dicarbaborane cages – new route to tricarbollide cages

“…[12][13][14][15] on degradative insertion of the aldehyde carbon into the structure of the [6-HO-arachno-B 10 H 13 ] 2-dianion and some metal-carbonyl C-insertion reactions [16][17][18] suggested that some specific C≡O -carbon incorporation procedures might be, in principle, applicable to other cluster systems. This viable synthetic approaches have been recently followed by our group, which led to developing a new carbon-incorporation strategy based on interaction between acyl chlorides (RCOCl) and the arachno-6,9-C 2 B 8 H 14 dicarbaborane in the presence of amine bases [19,20].…”