36988-93-9

Upstream product

• 16872-09-6 1,2-dicarba-closo-dodecaborane⁽¹²⁾ 
• 1079-66-9 chloro-diphenylphosphine 
• 109-72-8 n-butyllithium 
• 23841-96-5 1-lithium-1,2-dicarba-closo-dodecaborane⁽¹²⁾ 
• 12126-50-0 bis(pentamethylcyclopentadienyl)iron(II) 

Downstream Products

• 330581-19-6 1-lithio-2-diphenylphosphino-1,2-carborane 
• 943612-27-9 B₁₀H₁₀CHCP(C₆H₅)2CH₃⁽¹⁺⁾*I^(1-)=B₁₀H₁₀CHCP(C₆H₅)2CH₃I 
• 1334999-47-1 [1-(2′-(S)PPh2)-o-carborane] 

Relevant academic research and scientific papers

Carborane Stabilized 19-Electron Molybdenum Metalloradical

Paramagnetic metal complexes gained a lot of attention due to their participation in a number of important chemical reactions. In most cases, these complexes are dominated by 17-e metalloradicals that are associatively activated with highly reactive paramagnetic 19-e species. Molybdenum paramagnetic complexes are among the most investigated ones. While some examples of persistent 17-e Mo-centered radicals have been reported, in contrast, 19-e Mo-centered radicals are illusive species and as such could rarely be detected. In this work, the photodissociation of the [Cp(CO)3Mo]2 dimer (1) in the presence of phosphines was revisited. As a result, the first persistent, formally 19-e Mo radical with significant electron density on the Mo center (22%), Cp(CO)3Mo·PPh2(o-C2B10H11) (5b), was generated and characterized by EPR spectroscopy and MS as well as studied by DFT calculations. The stabilization of 5b was likely achieved due to a unique electron-withdrawing effect of the o-carboranyl substituent at the phosphorus center.

Neutral and zwitterionic half-sandwich Ir, Rh complexes supported by P,S-substituted o-carboranyl ligands: Synthesis, characterization and reactivity

The neutral Cp*M(Cl)(1-PPh2-2-S-1,2-C2B 10H10) and zwitterionic Cp*M(3-OCH 3-7-PPh2-8-S-7,8-C2B9H9) (Cp* = η5-C5Me5, M = Ir, Rh, 1-PPh2-2-S-1,2-C2B10H10 = [1-(diphenylphosphino)-2-thiolato)-1,2-dicarba-closo-carborane], 3-OCH 3-7-PPh2-8-S-7,8-C2B9H9 = [3-(methoxyl)-7-(diphenylphosphino)-8-(thiolato)-7,8-dicarba-nido-carborane] -) were synthesized and fully characterized. The 18-electron neutral closo-carborane complexes Cp*M(Cl)(1-PPh2-2-S-1,2-C 2B10H10) (M = Ir (1a), Rh (1b)) can be easily deboronated to result in the formation of reactive 16-electron zwitterionic nido-carborane complexes [Cp*M(3-OCH3-7-PPh2-8-S-7, 8-C2B9H9)] (M = Ir (2a), Rh(2b)). The oxidation of 2b with O2 gas afforded the corresponding sulfone complex 3b in high yields. Utilization of its unsaturated feature in 16-electron zwitterionic nido-carborane complexes offers a potential strategy to synthesize new types of organometallic complexes.

CARBORANE-PHOSPHONIUM COMPOUNDS AND THEIR USE IN BORON NEUTRON CAPTURE THERAPY AND IMAGING

The invention describes compounds for use in BCNT. These compounds comprise a carborane group coupled to a phosphorus containing group. The compounds may comprise a carborane group coupled to a phosphonium group.

Synthesis, Structure, and DFT Calculation of (Phosphino-o-carboranyl)silyl Group 10 Metal Complexes: Formation of Stable trans-Bis(P,Si-chelate)metal Complexes

Addition of the silane (HSiMe2)C2B10H 10(PR2) (R = Me (2a), OEt (2b)) to (PPh3) 2Pt(CH2-CH2) (3) affords the trans-bis(chelates) Pt(CabP,Si)2 (4a,b; Cab P,Si = η2-[(SiMe2)(PR2)C 2B10H10P,Si]) in high yield; the same product was also formed from Pt(cod)2 (9), as confirmed by NMR spectroscopy (1H, 31P). Using Pd2(dba)3 (6), the analogue trans-bis(chelate) Pd(Cabp,st)2 (7a) was obtained as a mixture of trans and cis isomers in which the former predominates, as established by NMR spectroscopy (1H, 31P). Thus, a series of kinetically stabilized transbis(chelate) metal complexes, trans-(CabP,Si)2M. (M = Pt (4a,b), Pd (7a)), bearing bulky o-carboranylphosphine tethers, were synthesized from the reaction of phosphinosilanes (2) with d10 metal complexes. In the presence of dimethyl acetylenedicarboxylate (DMAD), the trans isomer 4a,b thermally rearranges to the thermodynamically favored cis isomer cis(Cab P,Si)2Pt (5a,b). In addition, the oxidative addition of the Si-H bond to the sterically bulky diphenylphosphino silane (HSiMe 2)C2B10H10(PPh2) (2c) by 3 can be controlled to produce the mono(chelate) species (Cab P,Si)Pt(H)(PPh3) (10a). The related mono(chelate) product (CabP,Si)Pt(H)(CabP) (10b; CabP = (PPh 2)C2B10H11) results from the oxidative addition of 2c by 3, in which one PPhs ligand is displaced by Cab P. The structures of compounds 4a, 5a,c, 8c, and 10a,b were determined using single-crystal X-ray crystallography.

Kinetically stabilized P,Si-chelate metal complexes: isolation, isomerization, and X-ray structural analysis

A series of kinetically stabilized trans bis-chelate metal complexes, trans-(CabP,Si)2M (M = Pt 4; M = Pd 7a), bearing bulky o-carboranylphosphine tethers, have been synthesized from the reaction of the phosphinosilanes 2 with d10 metal complexes. In the presence of dimethyl acetylenedicarboxylate (DMAD), the trans isomer 4 thermally rearranges to the thermodynamically favored cis isomer, cis-(CabP,Si)2Pt 5.