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Publication Type
Journal Article
UWI Author(s)
Author, Analytic
Bakir, Mohammed/ A./Conry, Rebecca
Author Affiliation, Ana.
n/a
Article Title
Synthesis, spectroscopic and X-ray crystallographic properties of manganese compounds of keto- and enol-coordinated di-2-pyridyl ketone benzoyl hydrazone (dpkbh). Reactions of [Mn(CO)5 Br] with dpkbh
Medium Designator
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Connective Phrase
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Journal Title
Journal of Coordination Chemistry
Translated Title
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Reprint Status
Refereed
Date of Publication
March 2016
Volume ID
69
Issue ID
7
Page(s)
1244-1257
Language
n/a
Connective Phrase
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Location/URL
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ISSN
n/a
Notes
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Abstract
Reactions between [Mn(CO)5Br] and dpkbh in low boiling solvents in air gave fac-[MnI(CO)3(?2-Npy,Nim-dpkbh)Br]H2O, [MnIIBr2(?3-Npy,Nim,O-dpkbh)], and [MnII(?3-Npy,Nim,O-dpkbh-H)2]0.5H2O (Nim = imine nitrogen and Npy = pyridyl nitrogen). Crystallization of fac-[MnI(CO)3(?2-Npy,Nim-dpkbh)Br]H2O from dmso or CH3CN produced dark red crystals of [MnII(?3-Npy,Nim,O-dpkbh-H)2]nX (X = dmso, n = 1 and X = H2O, n = 0.22). This is in contrast to the reaction of [Re(CO)5Cl] with dpkbh in refluxing toluene to form fac-[ReI(CO)3(?2-,Npy,Npy-dpkbh)Cl] which can be crystallized from CH3CN, dmso or dmf to form fac-[ReI(CO)3(?2-,Npy,Npy-dpkbh)Cl]nX (X = CH3CN, n = 0 and solvate = dmso or dmf, n = 1). Infrared spectral measurements are consistent with keto coordination of dpkbh to Mn(I) in fac-[MnI(CO)3(?2-Npy,Nim-dpkbh)Br]H2O and Mn(II) in [MnIIBr2(?3-Npy,Nim,O-dpkbh)] plus enol coordination of the amide-deprotonated dpkbh, to the Mn(II) center in [MnII(?3-Npy,Nim,O-dpkbh-H)2]0.5H2O. Electronic absorption spectral measurements in non-aqueous solvents indicate sensitivity of fac-[MnI(CO)3(?2-Npy,Nim-dpkbh)Br]H2O and [MnII(?3-Npy,Nim,O-dpkbh-H)2]0.5H2O to changes in their outer-shell environments. X-ray crystallographic analyses elucidated the identities of [MnIIBr2(?3-Npy,Nim,O-dpkbh)] and [MnII(?3-Npy,Nim,O-dpkbh-H)2]nX and divulged weaker coordination of [dpkbh] to Mn(II) in [MnIIBr2(?3-Npy,Nim,O-dpkbh)] and stronger coordination of [dpkbh-H]- to Mn(II) in [MnII(?3-Npy,Nim,O-dpkbh-H)2]0.22H2O. Low-temperature X-ray structural analyses were employed to account for the disorder in the structure of [MnII(?3-Npy,Nim,O-dpkbh-H)2] and the short NH bond distance observed in the structure of [MnIIBr2(?3-Npy,Nim,O-dpkbh)]. A PLATON Squeeze treatment was invoked to account for the fractional occupancy of lattice water in the structure of [MnII(?3-Npy,Nim,O-dpkbh-H)2].....
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