Accessing the First nido‐Carborane‐Substituted Diphosphetane: A Ligand and Synthon for nido‐Carboranylphosphanes

Abstract

Deboronation of a carborane‐substituted diphosphetane 2 in toluene yielded the first nido‐carboranyldiphosphetane 1. The P−P bond in 1 can be broken via dismutation reactions with diaryl dichalcogenides yielding nido‐carboranyl bis‐phosphanes that were not accessible via established synthetic protocols. Additionally, transition metal complexes of 1 could be isolated including one coordination polymer. Notably, when the deboronation of 2 is carried out in ethanol, unprecedented nido‐carborane‐substituted secondary bis‐phosphane monoxides (3, 4) are obtained. These compounds are interesting starting materials for further reactivity studies due to their P−H bonds. Experimental findings are supported by DFT calculations including the calculation of reaction mechanisms and NMR spectroscopic parameters.

Dinuclear Palladium(II) and Platinum(II) Complexes of a Readily Accessible Bicyclic Diphosphane

“…Infrared spectra were recorded as KBr pellets on either a Perkin-Elmer System 2000 (4000-400 cm À 1 range) or a Spectrum 100 S (4000-250 cm À 1 range) Fourier-Transform spectrometer. 1 H (400 or 500 MHz) and 13 C{ 1 H} NMR (101 MHz) spectra were recorded on a Bruker DPX-400 FT or Jeol-ECZÀ R-500 spectrometer with chemical shifts (δ) in ppm to high frequency of Si(CH 3 ) 4 and coupling constants (J) in Hz. 31 P{ 1 H} NMR (162 or 202 MHz) spectra were recorded on a Bruker DPX-400 FT or Jeol-ECZ-R-500 spectrometer with chemical shifts (δ) in ppm to high frequency of 85 % H 3 PO 4 .…”

“…H), 3.54-3.48 (8H, m, PCH 2 N), 2.88 (12H, s, CH 3 ). 13 C{ 1 H} NMR (101 MHz): δ 145.8 (CNMe 2 ), 141.4 (CNH), 118.7 (C arom ), 114.5 (C arom ), 54.9 (CH 2 , t, J PC 16.9) 41.6 (NMe 2 ) ppm. 31 P{ 1 H} NMR (162 MHz): δ À 34.6 ppm.…”

“…Cummins and co-workers reported elegant routes to diphosphanes using transient "P 2 " or P 4 as phosphorus source. [9] Diphosphanes display various reactivities based on the ease of cleavage of the PÀ P bond, [10][11][12][13] a feature that continues to attract much interest.…”

“…All hydrogen atoms except NH and some MeCN solvent molecules of crystallisation not involved in Hbonds are omitted for clarity. Selected bond distances (Å) and angles (deg): Pt(1)À P(1) 2.2157(12), Pt(1)À P(2 A) 2.2107(13), Pt(1)À Cl(1) 2.3456(12), Pt(1)À Cl-(2) 2.3439(13), P(1)À P(2) 2.1875(17), F(8)À Pt(1) 3.457, F(8)À Pt(1 A) 3.560, F(8)À P(1) 3.071, F(8)À P(1 A) 3.227, F(8)À P(2) 3.167, F(8)À P(2 A) 3.139; Cl(1)À Pt-(1)À Cl(2) 91.71(5), P(1)À Pt(1)À P(2 A) 98.94(4). Symmetry operator: A = À x + 1, À y, À z + 1.…”

Intermolecular Cyclization between Carboranylphosphines and Electron-Deficient Alkynes

“…The compound nido -7,8-C 2 B 9 H 12 – and its derivatives, obtained by removing one boron vertex from closo -1,2- o -carboranes, are widely used mono anion carboranes. , The ionic nature of this type of compounds has enabled their use as counteranions in transition metal complexes. , Deprotonation of the mono anion affords the dianions nido -7,8-C 2 B 9 H 12 – , which are precursors to many closo metallacarboranes. , We have special interest in the application of nido -carboranes in phosphorus chemistry. In 2019, our group reported the first example of zwitterionic nido -carborane-fused phospholes, which are bright blue emitters (Scheme a) …”