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

24 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

Scopus Subject Areas

Catalysis
Organic Chemistry

User-Defined Keywords

O ligands
P ligands
Sulfates
Titanium
Zirconium

Access to Document

10.1002/chem.200400853

Cite this

@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 = "Wiley-VCH Verlag",

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 - http://www.scopus.com/inward/record.url?scp=19944429727&partnerID=8YFLogxK

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

Abstract

Scopus Subject Areas

User-Defined Keywords

Access to Document

Other files and links

Fingerprint

Cite this