Chemistry of Decaborane-Phosphorus Compounds. V. Bromocarboranes and Their Phosphination

Uncommon Coordination Behaviour of P(S) and P(Se) Units when Bonded to Carboranyl Clusters: Experimental and Computational Studies on the Oxidation of Carboranyl Phosphine Ligands

“…Slight differences in the P À C bonds originate from the aromatic and aliphatic carbon [53] are to high frequency. 10 33.82 [54] 1-OPiPr 2 -2-Me-1,2-closo-C 2 B 10 H 10 (4) 58.18 + 24.36 1-PPh 2 -2-Ph-1,2-closo-C 2 B 10 H 10 12.66 [56] 1-OPPh 2 -2-Ph-1,2-closo-C 2 B 10 H 10 (6) 19.65 + 6.99 1-SePPh 2 -2-Ph-1,2-closo-C 2 B 10 H 10 (18) 45.06 + 32.16 1-PiPr 2 -2-Ph-1,2-closo-C 2 B 10 H 10 38.50 [57] 1-OPiPr 2 -2-Ph-1,2-closo-C 2 B 10 H 10 (7) 53.27 + 14.77 1-PiPr 2 -1,2-closo-C 2 B 10 H 11 54.20 [18] 1-SPiPr 2 -1,2-closo-C 2 B 10 H 11 (13) 77.90 + 23.74 1-SePiPr 2 -1,2-closo-C 2 B 10 H 11 (16) 83.67 The structural analysis of 9 confirmed that only one of the two phosphorus atoms bonded to the closo cage was oxidized by sulfur (Figure 4and Table 3). The structure consists of well-separated entities with no short contacts between sulfur atoms of neighbouring molecules.…”

“…The electrophilic substitution chemistry of boron-substituted carboranes is in many ways reminiscent of that of arenes. [11] We are interested in the synthesis of carborane compounds containing exo-cluster substituents with lone pairs Abstract: Oxidation of closo-carboranyl diphosphines 1,2-(PR 2 ) 2 -1,2-closo-C 2 B 10 H 10 (R = Ph, iPr) and closo-carboranyl monophosphines 1-PR 2 -2-R'-1,2-closo-C 2 B 10 H 10 (R = Ph, iPr, Cy; R' = Me, Ph) with hydrogen peroxide, sulfur and elemental black selenium evidences the unique capacity of the closo-carborane cluster to produce uncommon or unprecedented P/P(E) (E = S, Se) and P=O/P=S chelating ligands. When H 2 O 2 reacts with 1,2-(PR 2 ) 2 -1,2-closo-C 2 B 10 H 10 (R = Ph, iPr), they are oxidized to 1,2-(OPR 2 ) 2 -1,2-closo-C 2 B 10 H 10 (R = Ph, iPr).…”

Balancing Steric and Electronic Effects in Carbonyl–Phosphine Molybdacarboranes

“…All other reagents were purchased from Sigma Aldrich Ltd. and also used without further purification. [1,2‐Me 2 ‐1,2‐ closo ‐C 2 B 10 H 10 ], [HNMe 3 ][7,8‐R 2 ‐7,8‐ nido ‐C 2 B 9 H 10 ] (R = H or Me), [Mo(CO) 2 (η‐C 3 H 5 )(MeCN) 2 Br] and [PNP][1,2‐Me 2 ‐3,3‐(CO) 2 ‐3‐(η‐C 3 H 5 )‐3,1,2‐ closo ‐MoC 2 B 9 H 9 ] were prepared by literature methods. NMR spectra were recorded with a Bruker DPX‐400 spectrometer; chemical shifts are reported relative to residual protonated solvent peaks ( 1 H, 13 C), or to external standards ( 11 B: BF 3 · OEt 2 , 31 P: H 3 PO 4 ).…”

Formation of closo-rhodacarboranes containing η2,η3-(CH2=CHC5H6) ligand in the reaction of μ-dichloro-bis[(η4-norbornadiene)rhodium] with nido-dicarbaundecaborates [K][nido-7-R1-8-R2-7,8-C2B9H10]

“…The resulting com pounds are stable in air, crystalline, yellow (3a) or orange (3b-d) substances, which are well soluble in organic sol vents and almost insoluble in hydrocarbons. All com pounds were characterized by the elemental analysis data, IR spectra, and 1 H and 11 B NMR spectra; for complexes 3a-c, 13 С{ 1 H} NMR spectra were additionally obtained (Table 1).…”