UNSPECIFIED (1991) STERICALLY HINDERED NICKEL(II) AND IRON(II) LACUNAR CYCLIDENE COMPLEXES CONTAINING GEM-DIMETHYL GROUPS ON THEIR SATURATED CHELATE RINGS. INORGANIC CHEMISTRY, 30 (13). pp. 2713-2724. ISSN 0020-1669.

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Abstract

The structure of the cyclidene ligand in the corresponding iron(II)-centered dioxygen carrier has been altered by the addition of gem-dimethyl groups to increase the bulk on the saturated rings of the parent macrocycle. Dramatic responses are found in the dioxygen affinities of the resulting complexes. Placing the bulky group to the rear of the cavity, within which the O2 binds, enhances the O2 affinity, while placing the group at the entry greatly decreases the affinity. The presence of bulky groups at both positions essentially stops the binding of O2. Interpretations are based on the crystal structure data and molecular modeling. X-ray structure data for [DMNiDM(Me2Me2Mxyl[16]cyclidene)](PF6)2: NiC32H48N6O2F12, monoclinic, P2(1)/c, a = 13.541 (4) angstrom, b = 15.408 (5) angstrom, c = 20.471 (7) angstrom, beta = 106.10-degrees, V = 4103 (2) angstrom 3, Z = 4, R = 0.083, and R(w) = 0.091 for 3302 reflections with I > 2.0-sigma.

Item Type:	Journal Article
Subjects:	Q Science > QD Chemistry
Journal or Publication Title:	INORGANIC CHEMISTRY
Publisher:	AMER CHEMICAL SOC
ISSN:	0020-1669
Official Date:	26 June 1991
Dates:	Date Event 26 June 1991 UNSPECIFIED
Volume:	30
Number:	13
Number of Pages:	12
Page Range:	pp. 2713-2724
Publication Status:	Published

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