| 词条 | 1,5-Diaza-3,7-diphosphacyclooctanes |
| 释义 |
Some metal-P{{sup|R}}{{sub|2}}N{{sup|R'}}{{sub|2}} complexes catalyze the production and oxidation of hydrogen (H{{sub|2}}). The catalytic mechanism involves the interaction of substrate with the amines in the second coordination sphere.[2][3] Synthesis and reactionsThe ligands are prepared by the condensation of a primary phosphine, formaldehyde, and a primary amine: 2 RPH{{sub|2}} + 4 CH{{sub|2}}O + 2 RNH{{sub|2}} → [RNCH{{sub|2}}P(R')CH{{sub|2}}]{{sub|2}} + 4 H{{sub|2}}O Diazadiphosphacyclooctanes function as chelating diphosphine ligands. Typical nickel complexes contain two such ligands are give the formula [Ni(P{{sup|R}}{{sub|2}}N{{sup|R'}}{{sub|2}}){{sub|2}}]{{sup|2+}}. Cationic complexes of these P{{sub|2}}N{{sub|2}} and related ligands often exhibit enhance reactivity toward H{{sub|2}}. These complexes serve as electrocatalysts for H{{sub|2}} production. Related ligandsAzadiphosphacycloheptanes are a related family of diphosphines, but containing only one amine. They are prepared by condensation of 1,2-bis(phenylphosphino)ethane, formaldehyde, and a primary amine.[4] From the meso-isomer, typical nickel complexes contain two such ligands, i.e. [Ni(P{{sup|R}}{{sub|2}}NR'){{sub|2}}]{{sup|2+}}. When bound to metals, these ligands adopt a conformation similar to that of 1,4-diazacycloheptanes. Acyclic phosphine-amine ligands have the formula (R{{sub|2}}PCH{{sub|2}})NR'. References1. ^{{cite journal|title=Synthesis of platinum, palladium and rhodium complexes of α-aminophosphine ligands|authors=Erika Bálint, Ádám Tajti, Anna Tripolszky, György Keglevich|year=2018|journal=Dalton Trans.|volume=47|pages=4755–4778|doi=10.1039/C8DT00178B}} {{DEFAULTSORT:Diaza-3, 7-diphosphacyclooctanes, 1, 5-}}2. ^{{cite journal|last1=Yang|first1=J. Y.|last2=Chen|first2=S.|last3=Dougherty|first3=W. G.|last4=Kassel|first4=W. S.|last5=Bullock|first5=R. M.|last6=DuBois|first6=D. L.|last7=Raugei|first7=S.|last8=Rousseau|first8=R.|last9=Dupuis|first9=M.|last10=Rakowski DuBois|first10=M.|title=Hydrogen oxidation catalysis by a nickel diphosphine complex with pendant tert-butyl amines|journal=Chem. Commun.|year=2010|pages=8618–8620|doi=10.1039/c0cc03246h}} 3. ^{{cite journal|last1=Bullock|first1=R. M.|last2=Helm|first2=M. L.|title=Molecular Electrocatalysts for Oxidation of Hydrogen Using Earth-Abundant Metals: Shoving Protons Around with Proton Relays|journal=Acc. Chem. Res.|year=2015|volume=48|pages=2017–2026|doi = 10.1021/acs.accounts.5b00069}} 4. ^{{cite journal|last1=Karasik|first1=A. A.|last2=Balueva|first2=A. S.|last3=Moussina|first3=E. I.|last4=Naumov|first4=R. N.|last5=Dobrynin|first5=A. B.|last6=Krivolapov|first6=D. B.|last7=Litvinov|first7=I. A.|last8=Sinyashin|first8=O. G.|title=1,3,6-azadiphosphacycloheptanes: a novel type of heterocyclic diphosphines|journal=Heteroatom Chemistry|year=2008|volume=19|pages=125–132|doi=10.1002/hc.20397}} 3 : Chelating agents|Bisphosphanes|Phosphorus heterocycles |
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