1,3,2‐Diselenaphospholanes with an Anellated Dicarba‐closo‐dodecaborane(12) Unit

Abstract

The reaction of the 1,2-diselenido-1,2-dicarba-closo-dodecaborane dianion (1) with dichloro(phenyl)phosphane affords the 1,3,2-diselenaphospholane (2) containing an anellated dicarbacloso-docecaborane(12) unit. The phospholane 2 was oxidised by reactions with the elements to the sulfide 3 and the selenide 4, and partial hydrolysis gave a selenophosphonic acid derivative 5 along with the bis(diselane) 6 and decomposition. The reaction of 2 with (ethene)bis(triphenylphosphane)platinum(0) displaces ethene and is accompanied by oxidative addition and rearrangement into the 851 bis(triphenylphosphane)platinum(II) complex 9, in which the chelating unit is linked to platinum via Pt-Se and Pt-P(Se) bonds, a rare example of a metallophosphane selenide. The molecular structures of 2 and 3 were determined by X-ray analysis. The solution-state structures of the new compounds follow from consistent multinuclear magnetic resonance data ( 1 H, 11 B, 13 C, 31 P, 77 Se, 195 Pt NMR).

Crystal structure of 1,3-bis[seleno(phenyl)-μ5-phospha]-3-selena-4,5-[1,2- dicarba-closo-dodecaborano(12)]-cyclopentane, Se[P(C6H5)Se]2(C2B10H10)

“…The reaction of the 1,2-diselenolato-1,2-dicarba-closo-dodecaborane(12) dianion [1,2-(1,2-C 2B10H10)Se2] 2 as the dilithio derivative with dichlorophenylphosphane in diethylether at 78°C and warming to ambient temperature affords the expected 1,3,2-diselanaphospha-cyclopentane as the major product [1] along with a small amount of another less soluble crystalline material. This was isolated and identified by X-ray structure analysis as the title compound.…”

1,3,2‐Diselenaborolanes with an Annelated Dicarba‐closo‐dodecaborane(12) Unit: Synthesis, Molecular Structure and Reactivity

“…The 77 Se NMR spectra are more enlightening in this respect, since at least in the cases of the boron halides 5-7, the 77 Se NMR signals are split into partially relaxed 1:1:1:1 quartets (Figure 1). In the cases of 3, 4, and 8, splitting due to 77 Se-11 B spin-spin coupling is not resolved in the 11 (Figure 2). This is in agreement with restricted rotation about the NC(iPr) bonds and a preference of the structure as determined for the crystalline material (see below).…”

“…Crystalline material was isolated for 15b (see below). Additional weak 11 B NMR signals, typical of tetracoordinate boron atoms, were observed for the reaction solutions and assigned to the boronium cations 17a (Figure 4, A) and 17b. From a mixScheme 6.…”

“…In addition to the typical set of four 11 B(carbor- Table 1. 13 C, 11 B, and 77 Se NMR spectroscopic data [a] of the carborane derivatives 3-9. [12] 614.1 [12] 445 ane) NMR signals, the 11 B NMR spectra clearly indicate the presence of three-coordinate boron, and each δ 11 B value is typical of the effect exerted by the respective substituent at the boron atom in the 1,3,2-diselenaborolane.…”

A Spirocyclic Borate and a Dihydroborate Derived from the 1,2‐Diselenolato‐1,2‐dicarba‐closo‐dodecaborane(12) Dianion [1,2‐(1,2‐C2B10H10)Se2]2–: Structures, NMR Spectroscopy, and DFT Calculations

“…The molecular structures of both borates as tetrabutylammonium salts were determined by X-ray analysis. In solution, the borates were characterized by multinuclear magnetic resonance spectroscopy ( 1 H, 11 B, 13 C, 77 Se). The gas-phase geometries of the borate anions were optimized [RB3LYP/ 6-3111+G(d,p) level of theory], and the NMR spectroscopic parameters (chemical shifts and coupling constants) were calculated.…”