Copper(I)/S(8) reversible reactions leading to an end-on bound dicopper(II) disulfide complex: nucleophilic reactivity and analogies to copper-dioxygen chemistry.

Copper(I)/S(8) reversible reactions leading to an end-on bound dicopper(II) disulfide complex: nucleophilic reactivity and analogies to copper-dioxygen chemistry. Research Abstract Details 

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Copper(I)/S(8) reversible reactions leading to an end-on bound dicopper(II) disulfide complex: nucleophilic reactivity and analogies to copper-dioxygen chemistry. Abstract Text:

Debabrata Maiti,Julia S Woertink,Michael A Vance,Ashley E Milligan,Amy A Narducci Sarjeant,Edward I Solomon,Kenneth D Karlin,

Elemental sulfur (S8) reacts reversibly with the copper(I) complex [(TMPA')CuI](+) (1), where TMPA' is a TMPA (tris(2-pyridylmethyl)amine) analogue with a 6-CH2OCH3 substituent on one pyridyl ligand arm, affording a spectroscopically pure end-on bound disulfido-dicopper(II) complex [{(TMPA')Cu(II)}2(mu-1,2-S2(2-))](2+) (2) {nu(S-S) = 492 cm(-1); nu(Cu-S)sym = 309 cm(-1)}; by contrast, [(TMPA)Cu(I)(CH3CN)](+) (3)/S8 chemistry produces an equilibrium mixture of at least three complexes. The reaction of excess PPh3 with 2 leads to formal "release" of zerovalent sulfur and reduction of copper ion to give the corresponding complex [(TMPA')Cu(I)(PPh3)](+) (11) along with S=PPh3 as products. Dioxygen displaces the disulfur moiety from 2 to produce the end-on Cu2O2 complex, [{(TMPA')Cu(II)}2(mu-1,2-O2(2-)](2+) (9). Addition of the tetradentate ligand TMPA to 2 generates the apparently more thermodynamically stable [{(TMPA)Cu(II)}2(mu-1,2-S2(2-))](2+) (4) and expected mixture of other species. Bubbling 2 with CO leads to the formation of the carbonyl adduct [(TMPA')CuI(CO)](+) (8). Carbonylation/sulfur-release/CO-removal cycles can be repeated several times. Sulfur atom transfer from 2 also occurs in a near quantitative manner when it is treated with 2,6-dimethylphenyl isocyanide (ArNC), leading to the corresponding isothiocyanate (ArNCS) and [(TMPA')Cu(I)(CNAr)](+) (12). Complex 2 readily reacts with PhCH2Br: [{(TMPA')Cu(II)}2(mu-1,2-S(2)(2-)](2+) (2) + 2 PhCH2Br --> [{(TMPA')Cu(II)(Br)}2](2+) (6) + PhCH2SSCH2Ph. The unprecedented substrate reactivity studies reveal that end-on bound mu-1,2-disulfide-dicopper(II) complex 2 provides a nucleophilic S2(2-) moiety, in striking contrast to the electrophilic behavior of a recently described side-on bound mu-eta(2):eta(2)-disulfido-dicopper(II) complex, [{(N3)Cu(II)}(2)(mu-eta(2):eta(2)-S2(2-))](2+) (5) with tridentate N3 ligand. The investigation thus reveals striking analogies of copper/sulfur and copper/dioxygen chemistries, with regard to structure type formation and specific substrate reactivity patterns.

Copper(I)/S(8) reversible reactions leading to an end-on bound dicopper(II) disulfide complex: nucleophilic reactivity and analogies to copper-dioxygen chemistry. Publishing Authors By Initials

D Maiti,JS Woertink,MA Vance,AE Milligan,AA Sarjeant,EI Solomon,KD Karlin,

For similar inorganic chemicals: elements: chalcogens: sulfur research abstracts see: inorganic chemicals: elements: chalcogens: sulfur research

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Copper(I)/S(8) reversible reactions leading to an end-on bound dicopper(II) disulfide complex: nucleophilic reactivity and analogies to copper-dioxygen chemistry. Journal Published:

PUBLICATION TYPE: Research Support, N.I.H., Extr

Journal: Journal of the American Chemical Society

VOLUME: 129

Page Numbers: 8882-92

Journal Abbreviation: J. Am. Chem. Soc.

ISSN: 0002-7863

DAY: 26

MONTH: 06

YEAR: 2007

Copper(I)/S(8) reversible reactions leading to an end-on bound dicopper(II) disulfide complex: nucleophilic reactivity and analogies to copper-dioxygen chemistry. Information

Number of References:

LANGUAGE: eng

NlmUniqueID: 7503056

Copper(I)/S(8) reversible reactions leading to an end-on bound dicopper(II) disulfide complex: nucleophilic reactivity and analogies to copper-dioxygen chemistry. Keywords Mesh Terms:

KEYWORDS: Sulfur

MESH TERMS: chemistry

Chemical & Substance for Abstract: Copper(I)/S(8) reversible reactions leading to an end-on bound dicopper(II) disulfide complex: nucleophilic reactivity and analogies to copper-dioxygen chemistry. Information

Substance Name: Sulfur

Registry Number: 7704-34-9

Grant and Affiliation Information for Copper(I)/S(8) reversible reactions leading to an end-on bound dicopper(II) disulfide complex: nucleophilic reactivity and analogies to copper-dioxygen chemistry.

AFFILIATION: Department of Chemistry, Johns Hopkins University, Baltimore, Maryland 21218, USA.

Country: United States

AGENCY: United States NIGMS

GRANT: GM28962

ACRONYM: GM

MEDLINETA: J Am Chem Soc

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