Synthesis, structure, and reactivity of homoleptic cerium(IV) and cerium(III) alkoxides

Ayusman Sen; Hilmar A. Steelier; Arnold L. Rheingold

doi:10.1021/ic00029a025

Synthesis, structure, and reactivity of homoleptic cerium(IV) and cerium(III) alkoxides

Ayusman Sen, Hilmar A. Steelier, Arnold L. Rheingold

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

73 Scopus citations

Abstract

The reaction of Ce(OC^tBu₃)₃(1) with the following oxidants has been studied: benzoyl peroxide, BzP; di-tert-butyl peroxide, DTBP; tert-butyl peroxybenzoate, BPB; benzoquinone, Bq; 2, 6-di-tert-butylbenzoquinone, DBBq. Ce(OC^tBu₃)₃(OC(O)Ph) (2) was formed in the reaction of 1 with BzP. 1 and DTBP reacted in 1:1 ratio to generate the unstable Ce(IV) species Ce(OC^tBu₃)₂(O^tBu)₂(3). On the other hand, a 1:0.5 ratio of reactants resulted in the formation of the Ce(III) compound [Ce(OC^tBu₃)₂(O^tBu)]₂(4). The X-ray crystal structure of 4 (P2₁/c; a = 11.783 (2) Å, b = 23.606 (6) Å, c = 11.544 (2) Å, β = 95.19 (2)°; 3240 independent reflections with F_o≥ 6γ(F_o); R(F) = 3.79%, R_w(F) = 4.08%; GOF = 1.126) indicated it to be dimeric with a pseudotetrahedral geometry around each cerium atom. The interconversions between 1, 3, and 4 were examined. The reaction of 1 with BPB caused the formation of equal amounts of 2 and 3. 1 was found to react with Bq to form (^tBu₃CO)₃CeOC₆H₄OCe(OC^tBu₃)₃(5). 5 was structurally characterized (Pi; a = 12.629 (4) Å, b = 12.736 (5) Å, c = 18.148 (8) Å, α = 83.60 (3)°, ς = 76.83 (3)°, γ = 61.57 (3)°; 6403 independent reflections with F_o≥ 5γ(F_o); R(F) = 7.70%, R_wF) = 7.97%; GOF = 1.466). The two cerium atoms in the molecule are bridged by a hydroquinonediolate moiety. As expected, the Ce(IV)-0 distances were shorter than the Ce(III)-O bond lengths. Finally, the reaction of 1 with DBBq resulted in the formation of the radical (^tBu₃CO)₃CeOC₆H₂^tBu₂O^-(6).

Original language	English (US)
Pages (from-to)	473-479
Number of pages	7
Journal	Inorganic chemistry
Volume	31
Issue number	3
DOIs	https://doi.org/10.1021/ic00029a025
State	Published - Feb 1 1992

All Science Journal Classification (ASJC) codes

Physical and Theoretical Chemistry
Inorganic Chemistry

Access to Document

10.1021/ic00029a025

Cite this

@article{56025be653014b1f955bcf8d79699454,

title = "Synthesis, structure, and reactivity of homoleptic cerium(IV) and cerium(III) alkoxides",

abstract = "The reaction of Ce(OCtBu3)3(1) with the following oxidants has been studied: benzoyl peroxide, BzP; di-tert-butyl peroxide, DTBP; tert-butyl peroxybenzoate, BPB; benzoquinone, Bq; 2, 6-di-tert-butylbenzoquinone, DBBq. Ce(OCtBu3)3(OC(O)Ph) (2) was formed in the reaction of 1 with BzP. 1 and DTBP reacted in 1:1 ratio to generate the unstable Ce(IV) species Ce(OCtBu3)2(OtBu)2(3). On the other hand, a 1:0.5 ratio of reactants resulted in the formation of the Ce(III) compound [Ce(OCtBu3)2(OtBu)]2(4). The X-ray crystal structure of 4 (P21/c; a = 11.783 (2) {\AA}, b = 23.606 (6) {\AA}, c = 11.544 (2) {\AA}, β = 95.19 (2)°; 3240 independent reflections with Fo≥ 6γ(Fo); R(F) = 3.79%, Rw(F) = 4.08%; GOF = 1.126) indicated it to be dimeric with a pseudotetrahedral geometry around each cerium atom. The interconversions between 1, 3, and 4 were examined. The reaction of 1 with BPB caused the formation of equal amounts of 2 and 3. 1 was found to react with Bq to form (tBu3CO)3CeOC6H4OCe(OCtBu3)3(5). 5 was structurally characterized (Pi; a = 12.629 (4) {\AA}, b = 12.736 (5) {\AA}, c = 18.148 (8) {\AA}, α = 83.60 (3)°, ς = 76.83 (3)°, γ = 61.57 (3)°; 6403 independent reflections with Fo≥ 5γ(Fo); R(F) = 7.70%, RwF) = 7.97%; GOF = 1.466). The two cerium atoms in the molecule are bridged by a hydroquinonediolate moiety. As expected, the Ce(IV)-0 distances were shorter than the Ce(III)-O bond lengths. Finally, the reaction of 1 with DBBq resulted in the formation of the radical (tBu3CO)3CeOC6H2tBu2O-(6).",

author = "Ayusman Sen and Steelier, {Hilmar A.} and Rheingold, {Arnold L.}",

year = "1992",

month = feb,

day = "1",

doi = "10.1021/ic00029a025",

language = "English (US)",

volume = "31",

pages = "473--479",

journal = "Inorganic chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "3",

}

TY - JOUR

T1 - Synthesis, structure, and reactivity of homoleptic cerium(IV) and cerium(III) alkoxides

AU - Sen, Ayusman

AU - Steelier, Hilmar A.

AU - Rheingold, Arnold L.

PY - 1992/2/1

Y1 - 1992/2/1

N2 - The reaction of Ce(OCtBu3)3(1) with the following oxidants has been studied: benzoyl peroxide, BzP; di-tert-butyl peroxide, DTBP; tert-butyl peroxybenzoate, BPB; benzoquinone, Bq; 2, 6-di-tert-butylbenzoquinone, DBBq. Ce(OCtBu3)3(OC(O)Ph) (2) was formed in the reaction of 1 with BzP. 1 and DTBP reacted in 1:1 ratio to generate the unstable Ce(IV) species Ce(OCtBu3)2(OtBu)2(3). On the other hand, a 1:0.5 ratio of reactants resulted in the formation of the Ce(III) compound [Ce(OCtBu3)2(OtBu)]2(4). The X-ray crystal structure of 4 (P21/c; a = 11.783 (2) Å, b = 23.606 (6) Å, c = 11.544 (2) Å, β = 95.19 (2)°; 3240 independent reflections with Fo≥ 6γ(Fo); R(F) = 3.79%, Rw(F) = 4.08%; GOF = 1.126) indicated it to be dimeric with a pseudotetrahedral geometry around each cerium atom. The interconversions between 1, 3, and 4 were examined. The reaction of 1 with BPB caused the formation of equal amounts of 2 and 3. 1 was found to react with Bq to form (tBu3CO)3CeOC6H4OCe(OCtBu3)3(5). 5 was structurally characterized (Pi; a = 12.629 (4) Å, b = 12.736 (5) Å, c = 18.148 (8) Å, α = 83.60 (3)°, ς = 76.83 (3)°, γ = 61.57 (3)°; 6403 independent reflections with Fo≥ 5γ(Fo); R(F) = 7.70%, RwF) = 7.97%; GOF = 1.466). The two cerium atoms in the molecule are bridged by a hydroquinonediolate moiety. As expected, the Ce(IV)-0 distances were shorter than the Ce(III)-O bond lengths. Finally, the reaction of 1 with DBBq resulted in the formation of the radical (tBu3CO)3CeOC6H2tBu2O-(6).

AB - The reaction of Ce(OCtBu3)3(1) with the following oxidants has been studied: benzoyl peroxide, BzP; di-tert-butyl peroxide, DTBP; tert-butyl peroxybenzoate, BPB; benzoquinone, Bq; 2, 6-di-tert-butylbenzoquinone, DBBq. Ce(OCtBu3)3(OC(O)Ph) (2) was formed in the reaction of 1 with BzP. 1 and DTBP reacted in 1:1 ratio to generate the unstable Ce(IV) species Ce(OCtBu3)2(OtBu)2(3). On the other hand, a 1:0.5 ratio of reactants resulted in the formation of the Ce(III) compound [Ce(OCtBu3)2(OtBu)]2(4). The X-ray crystal structure of 4 (P21/c; a = 11.783 (2) Å, b = 23.606 (6) Å, c = 11.544 (2) Å, β = 95.19 (2)°; 3240 independent reflections with Fo≥ 6γ(Fo); R(F) = 3.79%, Rw(F) = 4.08%; GOF = 1.126) indicated it to be dimeric with a pseudotetrahedral geometry around each cerium atom. The interconversions between 1, 3, and 4 were examined. The reaction of 1 with BPB caused the formation of equal amounts of 2 and 3. 1 was found to react with Bq to form (tBu3CO)3CeOC6H4OCe(OCtBu3)3(5). 5 was structurally characterized (Pi; a = 12.629 (4) Å, b = 12.736 (5) Å, c = 18.148 (8) Å, α = 83.60 (3)°, ς = 76.83 (3)°, γ = 61.57 (3)°; 6403 independent reflections with Fo≥ 5γ(Fo); R(F) = 7.70%, RwF) = 7.97%; GOF = 1.466). The two cerium atoms in the molecule are bridged by a hydroquinonediolate moiety. As expected, the Ce(IV)-0 distances were shorter than the Ce(III)-O bond lengths. Finally, the reaction of 1 with DBBq resulted in the formation of the radical (tBu3CO)3CeOC6H2tBu2O-(6).

UR - http://www.scopus.com/inward/record.url?scp=0001721484&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0001721484&partnerID=8YFLogxK

U2 - 10.1021/ic00029a025

DO - 10.1021/ic00029a025

M3 - Article

AN - SCOPUS:0001721484

SN - 0020-1669

VL - 31

SP - 473

EP - 479

JO - Inorganic chemistry

JF - Inorganic chemistry

IS - 3

ER -

Synthesis, structure, and reactivity of homoleptic cerium(IV) and cerium(III) alkoxides

Abstract

All Science Journal Classification (ASJC) codes

Access to Document

Other files and links

Fingerprint

Cite this