Titanium(IV) and zirconium(IV) sulfato complexes containing the Kläui tripodal ligand: Molecular models of sulfated metal oxide surfaces

Qian Feng Zhang; Tony C.H. Lam; Xiao Yi Yi; Eddie Y.Y. Chan; Wai Yeung Wong; Herman H.Y. Sung; Ian D. Williams; Wa Hung Leung

doi:10.1002/chem.200400853

Titanium(IV) and zirconium(IV) sulfato complexes containing the Kläui tripodal ligand: Molecular models of sulfated metal oxide surfaces

Qian Feng Zhang
, Tony C.H. Lam
, Xiao Yi Yi
, Eddie Y.Y. Chan
, Wai Yeung Wong
, Herman H.Y. Sung
, Ian D. Williams
, Wa Hung Leung^*

^*Corresponding author for this work

Department of Chemistry

Research output: Contribution to journal › Journal article › peer-review

25 Citations (Scopus)

Abstract

Treatment of titanyl sulfate in about 60 nM sulfuric acid with NaL, (L _OEt = [(η⁵-C₅H₅)Co-{(P(O)(OEt) ₂}₃]^-) afforded the μ-sulfato complex [(L_OEtOEtTi)₂(μ-O)₂(μ-SO ₄)] (2). In more concentrated sulfuric acid (> 1 M), the same reaction yielded the di-μ-sulfato complex [(L_OEtTi) ₂(μ-O)(μ-SO₄)₂] (3). Reaction of 2 with HOTf (OTf = triflate, CF₃SO₃) gave the tris-(triflato) complex [L_OEtTi(OTf)₃] (4), whereas treatment of 2 with Ag(OTf) in CH₂Cl₂ afforded the sulfato-capped trinuclear complex [{(L_OEt)₃Ti₃(μ-O) ₃}(μ₃-SO₄){Ag(OTf)}][OTf] (5), in which the Ag(OTf) moiety binds to a μ-oxo group in the Ti₃(μ-O) ₃ core. Reaction of 2 in H₂O with Ba(NO₃) ₂ afforded the tetranuclear complex (L_OEt) ₄Ti₄(μ-O)₆ (6). Treatment of 2 with [{Rh(cod)Cl}₂] (cod = 1,5-cyclooctadiene), [Re(CO)₅Cl], and [Ru(tBu₂-bpy)(PPh₃)₂Cl₂] (tBu₂bpy = 4,4′-dl-tert-butyl-2,2′-dipyridyl) in the presence of Ag(OTf) afforded the heterometallic complexes [(L _OEt)₂Ti₂(O)₂(SO₄){Rh- (cod)}₂][OTf]₂ (7), [(L_OEt)₂Ti(O) ₂-(SO₄){Re(CO)₃}][OTf] (8), and [{(L _OEt)₂Ti₂(μ-O)}(μ₃-SO ₄)(μ-O)₂{Ru-(PPh₃)(tBu₂bpy)}] [OTf]₂ (9), respectively. Complex 9 is paramagnetic with a measured magnetic moment of about 2.4 μ_B. Treatment of zirconyl nitrate with NaL_OEt in 3.5 M sulfuric acid afforded [(L_OEt) ₂Zr(NO₃)][L_OEtZr(SO₄)-(NO ₃)] (10). Reaction of ZrCl₄ in 1.8 M sulfuric acid with NaL_OEt in the presence Na₂SO₄ gave the μ-sulfato-bridged complex [L_OEtZr(SO₄)(H ₂O)]₂(μ-SO₄) (11). Treatment of 11 with triflic acid afforded [(L_OEt)₂Zr][OTf]₂ (12), whereas reaction of 11 with Ag(OTf) afforded a mixture of 12 and trinuclear [{L_OEtZr(SO₄)(H₂O)}₃(μ ₃-SO₄)][OTf] (13). The Zr^IV triflato complex [L_OEtZr-(OTf)₃] (14) was prepared by reaction of L _OEtZrF₃ with Me₃SiOTf. Complexes 4 and 14 can catalyze the Diels-Alder reaction of 1,3-cyclohexadiene with acrolein in good selectivity. Complexes 2-5, 9-11, and 13 have been characterized by X-ray crystallography.

Original language	English
Pages (from-to)	101-111
Number of pages	11
Journal	Chemistry - A European Journal
Volume	11
Issue number	1
DOIs	https://doi.org/10.1002/chem.200400853
Publication status	Published - 2005

User-Defined Keywords

O ligands
P ligands
Sulfates
Titanium
Zirconium

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10.1002/chem.200400853

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@article{40d6cc5a387a41f5ab1dae3a71680aa5,

title = "Titanium(IV) and zirconium(IV) sulfato complexes containing the Kl{\"a}ui tripodal ligand: Molecular models of sulfated metal oxide surfaces",

abstract = "Treatment of titanyl sulfate in about 60 nM sulfuric acid with NaL, (L OEt = [(η5-C5H5)Co-\{(P(O)(OEt) 2\}3]-) afforded the μ-sulfato complex [(LOEtOEtTi)2(μ-O)2(μ-SO 4)] (2). In more concentrated sulfuric acid (> 1 M), the same reaction yielded the di-μ-sulfato complex [(LOEtTi) 2(μ-O)(μ-SO4)2] (3). Reaction of 2 with HOTf (OTf = triflate, CF3SO3) gave the tris-(triflato) complex [LOEtTi(OTf)3] (4), whereas treatment of 2 with Ag(OTf) in CH2Cl2 afforded the sulfato-capped trinuclear complex [\{(LOEt)3Ti3(μ-O) 3\}(μ3-SO4)\{Ag(OTf)\}][OTf] (5), in which the Ag(OTf) moiety binds to a μ-oxo group in the Ti3(μ-O) 3 core. Reaction of 2 in H2O with Ba(NO3) 2 afforded the tetranuclear complex (LOEt) 4Ti4(μ-O)6 (6). Treatment of 2 with [\{Rh(cod)Cl\}2] (cod = 1,5-cyclooctadiene), [Re(CO)5Cl], and [Ru(tBu2-bpy)(PPh3)2Cl2] (tBu2bpy = 4,4′-dl-tert-butyl-2,2′-dipyridyl) in the presence of Ag(OTf) afforded the heterometallic complexes [(L OEt)2Ti2(O)2(SO4)\{Rh- (cod)\}2][OTf]2 (7), [(LOEt)2Ti(O) 2-(SO4)\{Re(CO)3\}][OTf] (8), and [\{(L OEt)2Ti2(μ-O)\}(μ3-SO 4)(μ-O)2\{Ru-(PPh3)(tBu2bpy)\}] [OTf]2 (9), respectively. Complex 9 is paramagnetic with a measured magnetic moment of about 2.4 μB. Treatment of zirconyl nitrate with NaLOEt in 3.5 M sulfuric acid afforded [(LOEt) 2Zr(NO3)][LOEtZr(SO4)-(NO 3)] (10). Reaction of ZrCl4 in 1.8 M sulfuric acid with NaLOEt in the presence Na2SO4 gave the μ-sulfato-bridged complex [LOEtZr(SO4)(H 2O)]2(μ-SO4) (11). Treatment of 11 with triflic acid afforded [(LOEt)2Zr][OTf]2 (12), whereas reaction of 11 with Ag(OTf) afforded a mixture of 12 and trinuclear [\{LOEtZr(SO4)(H2O)\}3(μ 3-SO4)][OTf] (13). The ZrIV triflato complex [LOEtZr-(OTf)3] (14) was prepared by reaction of L OEtZrF3 with Me3SiOTf. Complexes 4 and 14 can catalyze the Diels-Alder reaction of 1,3-cyclohexadiene with acrolein in good selectivity. Complexes 2-5, 9-11, and 13 have been characterized by X-ray crystallography.",

keywords = "O ligands, P ligands, Sulfates, Titanium, Zirconium",

author = "Zhang, \{Qian Feng\} and Lam, \{Tony C.H.\} and Yi, \{Xiao Yi\} and Chan, \{Eddie Y.Y.\} and Wong, \{Wai Yeung\} and Sung, \{Herman H.Y.\} and Williams, \{Ian D.\} and Leung, \{Wa Hung\}",

year = "2005",

doi = "10.1002/chem.200400853",

language = "English",

volume = "11",

pages = "101--111",

journal = "Chemistry - A European Journal",

issn = "0947-6539",

publisher = "John Wiley \& Sons Ltd",

number = "1",

}

TY - JOUR

T1 - Titanium(IV) and zirconium(IV) sulfato complexes containing the Kläui tripodal ligand

T2 - Molecular models of sulfated metal oxide surfaces

AU - Zhang, Qian Feng

AU - Lam, Tony C.H.

AU - Yi, Xiao Yi

AU - Chan, Eddie Y.Y.

AU - Wong, Wai Yeung

AU - Sung, Herman H.Y.

AU - Williams, Ian D.

AU - Leung, Wa Hung

PY - 2005

Y1 - 2005

N2 - Treatment of titanyl sulfate in about 60 nM sulfuric acid with NaL, (L OEt = [(η5-C5H5)Co-{(P(O)(OEt) 2}3]-) afforded the μ-sulfato complex [(LOEtOEtTi)2(μ-O)2(μ-SO 4)] (2). In more concentrated sulfuric acid (> 1 M), the same reaction yielded the di-μ-sulfato complex [(LOEtTi) 2(μ-O)(μ-SO4)2] (3). Reaction of 2 with HOTf (OTf = triflate, CF3SO3) gave the tris-(triflato) complex [LOEtTi(OTf)3] (4), whereas treatment of 2 with Ag(OTf) in CH2Cl2 afforded the sulfato-capped trinuclear complex [{(LOEt)3Ti3(μ-O) 3}(μ3-SO4){Ag(OTf)}][OTf] (5), in which the Ag(OTf) moiety binds to a μ-oxo group in the Ti3(μ-O) 3 core. Reaction of 2 in H2O with Ba(NO3) 2 afforded the tetranuclear complex (LOEt) 4Ti4(μ-O)6 (6). Treatment of 2 with [{Rh(cod)Cl}2] (cod = 1,5-cyclooctadiene), [Re(CO)5Cl], and [Ru(tBu2-bpy)(PPh3)2Cl2] (tBu2bpy = 4,4′-dl-tert-butyl-2,2′-dipyridyl) in the presence of Ag(OTf) afforded the heterometallic complexes [(L OEt)2Ti2(O)2(SO4){Rh- (cod)}2][OTf]2 (7), [(LOEt)2Ti(O) 2-(SO4){Re(CO)3}][OTf] (8), and [{(L OEt)2Ti2(μ-O)}(μ3-SO 4)(μ-O)2{Ru-(PPh3)(tBu2bpy)}] [OTf]2 (9), respectively. Complex 9 is paramagnetic with a measured magnetic moment of about 2.4 μB. Treatment of zirconyl nitrate with NaLOEt in 3.5 M sulfuric acid afforded [(LOEt) 2Zr(NO3)][LOEtZr(SO4)-(NO 3)] (10). Reaction of ZrCl4 in 1.8 M sulfuric acid with NaLOEt in the presence Na2SO4 gave the μ-sulfato-bridged complex [LOEtZr(SO4)(H 2O)]2(μ-SO4) (11). Treatment of 11 with triflic acid afforded [(LOEt)2Zr][OTf]2 (12), whereas reaction of 11 with Ag(OTf) afforded a mixture of 12 and trinuclear [{LOEtZr(SO4)(H2O)}3(μ 3-SO4)][OTf] (13). The ZrIV triflato complex [LOEtZr-(OTf)3] (14) was prepared by reaction of L OEtZrF3 with Me3SiOTf. Complexes 4 and 14 can catalyze the Diels-Alder reaction of 1,3-cyclohexadiene with acrolein in good selectivity. Complexes 2-5, 9-11, and 13 have been characterized by X-ray crystallography.

AB - Treatment of titanyl sulfate in about 60 nM sulfuric acid with NaL, (L OEt = [(η5-C5H5)Co-{(P(O)(OEt) 2}3]-) afforded the μ-sulfato complex [(LOEtOEtTi)2(μ-O)2(μ-SO 4)] (2). In more concentrated sulfuric acid (> 1 M), the same reaction yielded the di-μ-sulfato complex [(LOEtTi) 2(μ-O)(μ-SO4)2] (3). Reaction of 2 with HOTf (OTf = triflate, CF3SO3) gave the tris-(triflato) complex [LOEtTi(OTf)3] (4), whereas treatment of 2 with Ag(OTf) in CH2Cl2 afforded the sulfato-capped trinuclear complex [{(LOEt)3Ti3(μ-O) 3}(μ3-SO4){Ag(OTf)}][OTf] (5), in which the Ag(OTf) moiety binds to a μ-oxo group in the Ti3(μ-O) 3 core. Reaction of 2 in H2O with Ba(NO3) 2 afforded the tetranuclear complex (LOEt) 4Ti4(μ-O)6 (6). Treatment of 2 with [{Rh(cod)Cl}2] (cod = 1,5-cyclooctadiene), [Re(CO)5Cl], and [Ru(tBu2-bpy)(PPh3)2Cl2] (tBu2bpy = 4,4′-dl-tert-butyl-2,2′-dipyridyl) in the presence of Ag(OTf) afforded the heterometallic complexes [(L OEt)2Ti2(O)2(SO4){Rh- (cod)}2][OTf]2 (7), [(LOEt)2Ti(O) 2-(SO4){Re(CO)3}][OTf] (8), and [{(L OEt)2Ti2(μ-O)}(μ3-SO 4)(μ-O)2{Ru-(PPh3)(tBu2bpy)}] [OTf]2 (9), respectively. Complex 9 is paramagnetic with a measured magnetic moment of about 2.4 μB. Treatment of zirconyl nitrate with NaLOEt in 3.5 M sulfuric acid afforded [(LOEt) 2Zr(NO3)][LOEtZr(SO4)-(NO 3)] (10). Reaction of ZrCl4 in 1.8 M sulfuric acid with NaLOEt in the presence Na2SO4 gave the μ-sulfato-bridged complex [LOEtZr(SO4)(H 2O)]2(μ-SO4) (11). Treatment of 11 with triflic acid afforded [(LOEt)2Zr][OTf]2 (12), whereas reaction of 11 with Ag(OTf) afforded a mixture of 12 and trinuclear [{LOEtZr(SO4)(H2O)}3(μ 3-SO4)][OTf] (13). The ZrIV triflato complex [LOEtZr-(OTf)3] (14) was prepared by reaction of L OEtZrF3 with Me3SiOTf. Complexes 4 and 14 can catalyze the Diels-Alder reaction of 1,3-cyclohexadiene with acrolein in good selectivity. Complexes 2-5, 9-11, and 13 have been characterized by X-ray crystallography.

KW - O ligands

KW - P ligands

KW - Sulfates

KW - Titanium

KW - Zirconium

UR - https://www.scopus.com/pages/publications/19944429727

U2 - 10.1002/chem.200400853

DO - 10.1002/chem.200400853

M3 - Journal article

AN - SCOPUS:19944429727

SN - 0947-6539

VL - 11

SP - 101

EP - 111

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 1

ER -

Titanium(IV) and zirconium(IV) sulfato complexes containing the Kläui tripodal ligand: Molecular models of sulfated metal oxide surfaces

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