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Combining Solid-state and Solution-based Techniques: Synthesis and Reactivity of ChalcogenidoplumbatesII or IV
Published on: December 29, 2016
Magnesium(0) complexes and their reduction reactions with binary transition metal carbonyls
Yixiao Jiang1, Maryam Niksefat1, Sophie G Unsworth1
1School of Chemistry, Monash University PO Box 23 VIC 3800 Australia http://www.monash.edu/science/research-groups/chemistry/jonesgroup.
None:
Three very bulky β-diketimine protio-ligands (ArNacnacH, {(Ar)N[double bond, length as m-dash]C(Bu t )}2CH2, Ar = 2,4,6-tricyclohexylphenyl TCHP; 2,6-dicyclohexylphenyl DCHP; TCHP/Dip, Dip = 2,6-diisopropylphenyl) have been synthesised. These have been used to prepare monomeric, three-coordinate β-diketiminato magnesium iodide complexes, [(ArNacnac)MgI] (Ar = TCHP 1, DCHP 3, or TCHP/Dip 5). Sodium metal reduction of 1 afforded the thermally robust anionic magnesium(0) complex [{(TCHPNacnac)Mg}Na]26 in good yield. In contrast, reduction of less bulky [(DCHPNacnac)MgI] 3 gave a mixture of unknown products, whilst reduction of [(TCHP/DipNacnac)MgI] 5 yielded the mixed oxidation state magnesium compound, [{(TCHP/DipNacnac)Mg}2Mg] 7. The related compound [{(TCHPNacnac)Mg}2Mg] 8, was prepared by reduction of a 2 : 1 mixture of [(TCHPNacnac)MgI] 1 and MgI2. Computational analyses of 6 and 8 reveal their electronic structures to be comparable to those of previously reported analogues of these compounds. Reduction reactions between magnesium(0) compound 6 and the neutral groups 6 and 7 transition metal carbonyls, Cr(CO)6, Mo(CO)6 and Mn2(CO)10, gave a series of complexes [{(TCHPNacnac)Mg}2{µ-M2(CO) n }] (n = 10, M = Cr 9 or Mo 10; n = 8, M = Mn 11) which incorporate metal-metal single (9 and 10) or double (11) bonded metal carbonyl fragments. In contrast, reduction of Fe(CO)5 with 6 yielded [{(TCHPNacnac)Mg}Na{Fe(CO)4}]212 which does not possess an Fe-Fe bond, and can be viewed as an analogue of Collman's reagent, Na2[Fe(CO)4], in which one Na+ cation has been replaced by a [(TCHPNacnac)Mg]+ unit.
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