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Title: The synthesis of PNP-supported low-spin nitro manganese(I) carbonyl complexes

In this study, the coordination chemistry of Mn(CO) 5Br was investigated with a series of PNP-pincer ligands. The ligands iPrPONOP ( iPrPONOP = 2,6-bis(diisopropylphosphinito)pyridine) and iPrPN HP ( iPrPN HP = HN{CH 2CH 2(PiPr 2)} 2) gave the desired organometallic manganese complexes ( iPrPONOP)Mn(CO) 2Br and ( iPrPN HP)Mn(CO) 2Br, respectively, upon chelation to Mn(CO) 5Br. The reactivity of iPrPNNNP ( iPrPNNNP = N,N'-bis(diisopropylphosphino)-2,6-diaminopyridine) with Mn(CO) 5Br yielded a pair of products, [( iPrPNNNP)Mn(CO) 3][Br] and ( iPrPNNNCO)Mn(CO) 3. The formation of the asymmetric chelate arises from a formal loss of iPr 2PBr and C–N bond formation from a carbonyl ligand and NH, yielding a Mn(I) amide core. The nitration reactions of ( iPrPONOP)Mn(CO) 2Br and ( iPrPN HP)Mn(CO) 2Br were carried out using silver nitrite, yielding the nitro compounds ( iPrPONOP)Mn(CO) 2(NO 2) and ( iPrPN HP)Mn(CO) 2(NO 2), respectively. The analogous iron complex ( iPrPONOP)Fe(CO)Cl 2 was nitrated under the same conditions to yield the salt pair [( iPrPONOP)Fe(CO) 2][FeCl 3NO]. This reactivity underlines the difference between iso-valent iron and manganese centers. The manganese complexes ( iPrPONOP)Mn(CO) 2(NO 2) and ( iPrPN HP)Mn(CO) 2(NO 2) were ineffective as oxygen atom transfer reagents for a variety of substrates.
Authors:
 [1] ;  [1]
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Publication Date:
Report Number(s):
LA-UR-16-20260
Journal ID: ISSN 0277-5387
Grant/Contract Number:
AC52-06NA25396
Type:
Accepted Manuscript
Journal Name:
Polyhedron
Additional Journal Information:
Journal Name: Polyhedron; Journal ID: ISSN 0277-5387
Publisher:
Elsevier
Research Org:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org:
USDOE
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1255273