Synthesis and Structural Characterization of a Neutral Lacunar Complex Formed by Deprotonation of Methyl Groups of the Cyclidene Macrocycle

Kenneth A. Goldsby; Alan J. Jircitano; Dennis L. Nosco; James C. Stevens; Daryle H. Busch

doi:10.1021/ic00338a027

Synthesis and Structural Characterization of a Neutral Lacunar Complex Formed by Deprotonation of Methyl Groups of the Cyclidene Macrocycle

Kenneth A. Goldsby, Alan J. Jircitano, Dennis L. Nosco, James C. Stevens, Daryle H. Busch

School of Science (Behrend)

Research output: Contribution to journal › Article › peer-review

7 Scopus citations

Abstract

X-ray structural analysis, electrochemistry, and reactivity with dioxygen are reported for the complex [Co{(CH₂)₂(MeN)₂-(CH₂)₆[16]cyclidene}]. The neutral complex is formed by deprotonation of the parent (CH₂)₆-bridged lacunar cyclidene complex. The structural differences between the parent and deprotonated complexes can be understood in terms of the redistribution of electron density upon deprotonation. The centralization of electron density and reduction in charge concomitant with deprotonation result in a large cathodic shift for the potential required to oxidize the cobalt(II) and structurally analogous nickel(II) complexes. The neutral cobalt(II) complex autoxidizes much faster than the corresponding cationic parent complex, and this has prevented dioxygen affinity measurements. [CO{(CH₂)₂(MeN)₂(CH₂)₆[16]cyclidene}] crystallized in the monoclinic system (P2₁/n) with unit cell dimensions a = 13.824 (2) Å, * = 11.351 (2) Å, c = 17.852 (2) Å, β = 115.16 (1)°, and Z = 4; R = 0.064 and Å* = 0.073 for 2666 observed reflections.

Original language	English (US)
Pages (from-to)	2523-2527
Number of pages	5
Journal	Inorganic chemistry
Volume	29
Issue number	13
DOIs	https://doi.org/10.1021/ic00338a027
State	Published - Jun 1 1990

All Science Journal Classification (ASJC) codes

Physical and Theoretical Chemistry
Inorganic Chemistry

Access to Document

10.1021/ic00338a027

Cite this

@article{5681f9617a3c482bad23a1d0f617ca0a,

title = "Synthesis and Structural Characterization of a Neutral Lacunar Complex Formed by Deprotonation of Methyl Groups of the Cyclidene Macrocycle",

abstract = "X-ray structural analysis, electrochemistry, and reactivity with dioxygen are reported for the complex [Co{(CH2)2(MeN)2-(CH2)6[16]cyclidene}]. The neutral complex is formed by deprotonation of the parent (CH2)6-bridged lacunar cyclidene complex. The structural differences between the parent and deprotonated complexes can be understood in terms of the redistribution of electron density upon deprotonation. The centralization of electron density and reduction in charge concomitant with deprotonation result in a large cathodic shift for the potential required to oxidize the cobalt(II) and structurally analogous nickel(II) complexes. The neutral cobalt(II) complex autoxidizes much faster than the corresponding cationic parent complex, and this has prevented dioxygen affinity measurements. [CO{(CH2)2(MeN)2(CH2)6[16]cyclidene}] crystallized in the monoclinic system (P21/n) with unit cell dimensions a = 13.824 (2) {\AA}, * = 11.351 (2) {\AA}, c = 17.852 (2) {\AA}, β = 115.16 (1)°, and Z = 4; R = 0.064 and {\AA}* = 0.073 for 2666 observed reflections.",

author = "Goldsby, {Kenneth A.} and Jircitano, {Alan J.} and Nosco, {Dennis L.} and Stevens, {James C.} and Busch, {Daryle H.}",

year = "1990",

month = jun,

day = "1",

doi = "10.1021/ic00338a027",

language = "English (US)",

volume = "29",

pages = "2523--2527",

journal = "Inorganic chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "13",

}

TY - JOUR

T1 - Synthesis and Structural Characterization of a Neutral Lacunar Complex Formed by Deprotonation of Methyl Groups of the Cyclidene Macrocycle

AU - Goldsby, Kenneth A.

AU - Jircitano, Alan J.

AU - Nosco, Dennis L.

AU - Stevens, James C.

AU - Busch, Daryle H.

PY - 1990/6/1

Y1 - 1990/6/1

N2 - X-ray structural analysis, electrochemistry, and reactivity with dioxygen are reported for the complex [Co{(CH2)2(MeN)2-(CH2)6[16]cyclidene}]. The neutral complex is formed by deprotonation of the parent (CH2)6-bridged lacunar cyclidene complex. The structural differences between the parent and deprotonated complexes can be understood in terms of the redistribution of electron density upon deprotonation. The centralization of electron density and reduction in charge concomitant with deprotonation result in a large cathodic shift for the potential required to oxidize the cobalt(II) and structurally analogous nickel(II) complexes. The neutral cobalt(II) complex autoxidizes much faster than the corresponding cationic parent complex, and this has prevented dioxygen affinity measurements. [CO{(CH2)2(MeN)2(CH2)6[16]cyclidene}] crystallized in the monoclinic system (P21/n) with unit cell dimensions a = 13.824 (2) Å, * = 11.351 (2) Å, c = 17.852 (2) Å, β = 115.16 (1)°, and Z = 4; R = 0.064 and Å* = 0.073 for 2666 observed reflections.

AB - X-ray structural analysis, electrochemistry, and reactivity with dioxygen are reported for the complex [Co{(CH2)2(MeN)2-(CH2)6[16]cyclidene}]. The neutral complex is formed by deprotonation of the parent (CH2)6-bridged lacunar cyclidene complex. The structural differences between the parent and deprotonated complexes can be understood in terms of the redistribution of electron density upon deprotonation. The centralization of electron density and reduction in charge concomitant with deprotonation result in a large cathodic shift for the potential required to oxidize the cobalt(II) and structurally analogous nickel(II) complexes. The neutral cobalt(II) complex autoxidizes much faster than the corresponding cationic parent complex, and this has prevented dioxygen affinity measurements. [CO{(CH2)2(MeN)2(CH2)6[16]cyclidene}] crystallized in the monoclinic system (P21/n) with unit cell dimensions a = 13.824 (2) Å, * = 11.351 (2) Å, c = 17.852 (2) Å, β = 115.16 (1)°, and Z = 4; R = 0.064 and Å* = 0.073 for 2666 observed reflections.

UR - http://www.scopus.com/inward/record.url?scp=0142102090&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0142102090&partnerID=8YFLogxK

U2 - 10.1021/ic00338a027

DO - 10.1021/ic00338a027

M3 - Article

AN - SCOPUS:0142102090

SN - 0020-1669

VL - 29

SP - 2523

EP - 2527

JO - Inorganic chemistry

JF - Inorganic chemistry

IS - 13

ER -

Synthesis and Structural Characterization of a Neutral Lacunar Complex Formed by Deprotonation of Methyl Groups of the Cyclidene Macrocycle

Abstract

All Science Journal Classification (ASJC) codes

Access to Document

Other files and links

Fingerprint

Cite this