Synthesis and characterisation of first row transition metal complexes of functionalized 1,2,4-benzothiadiazines

E.R. Clark; M.U. Anwar; B.J. Leontowicz; Y. Beldjoudi; J.J. Hayward; W.T.K. Chan; E.L. Gavey; M. Pilkington; E. Zysman-Colman; J.M. Rawson

doi:10.1039/c4dt01413h

Synthesis and characterisation of first row transition metal complexes of functionalized 1,2,4-benzothiadiazines

E.R. Clark, M.U. Anwar, B.J. Leontowicz, Y. Beldjoudi, J.J. Hayward, W.T.K. Chan, E.L. Gavey, M. Pilkington, E. Zysman-Colman, J.M. Rawson

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Abstract

Reaction of the novel ligand 3-(2′-pyridyl)-benzo-1,2,4-thiadiazine (L) with the transition metal chloride salts MCl₂·xH₂O (M^II= Mn, Fe, Co, Cu and Zn) in a 2 : 1 mole ratio afforded the mononuclear octahedral (high spin) complexes L₂MCl₂(1a–1e respectively) in which L binds in a chelate fashion via N(2) and the pyridyl N atoms. In the case of CuCl₂ the intermediate 1 : 1 four-coordinate complex LCuCl₂ (2) was also isolated which adopts a polymeric structure with pseudo-square planar molecules linked via long CuS contacts (d_Cu^…S = 2.938(1) Å) in the apical position. In the presence of non-interacting ions, 3 : 1 complexes are isolated, exemplified by the reaction of L with Fe(CF₃SO₃)₂ in a 3 : 1 ratio which affords the low spin complex [L₃Fe][CF₃SO₃]₂ (3). Reaction of L with VCl₃ in a 2 : 1 mole ratio under aerobic conditions afforded the vanadyl complex [L₂V(=O)Cl][Cl] (4).

Original language	English
Pages (from-to)	12996-13005
Number of pages	10
Journal	Dalton Transactions
Volume	43
Issue number	34
Early online date	9 Jul 2014
DOIs	https://doi.org/10.1039/c4dt01413h
Publication status	Published - 14 Sept 2014

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10.1039/c4dt01413h

Colman_2014_DalTrans_Synthesis_AM
© Royal Society of Chemistry 2014. This work is made available online in accordance with the publisher’s policies. This is the author created, accepted version manuscript following peer review and may differ slightly from the final published version. The final published version of this work is available at http://dx.doi.org/10.1039/C4DT01413H
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title = "Synthesis and characterisation of first row transition metal complexes of functionalized 1,2,4-benzothiadiazines",

abstract = "Reaction of the novel ligand 3-(2′-pyridyl)-benzo-1,2,4-thiadiazine (L) with the transition metal chloride salts MCl2·xH2O (MII = Mn, Fe, Co, Cu and Zn) in a 2 : 1 mole ratio afforded the mononuclear octahedral (high spin) complexes L2MCl2 (1a–1e respectively) in which L binds in a chelate fashion via N(2) and the pyridyl N atoms. In the case of CuCl2 the intermediate 1 : 1 four-coordinate complex LCuCl2 (2) was also isolated which adopts a polymeric structure with pseudo-square planar molecules linked via long CuS contacts (dCu…S = 2.938(1) {\AA}) in the apical position. In the presence of non-interacting ions, 3 : 1 complexes are isolated, exemplified by the reaction of L with Fe(CF3SO3)2 in a 3 : 1 ratio which affords the low spin complex [L3Fe][CF3SO3]2 (3). Reaction of L with VCl3 in a 2 : 1 mole ratio under aerobic conditions afforded the vanadyl complex [L2V(=O)Cl][Cl] (4).",

author = "E.R. Clark and M.U. Anwar and B.J. Leontowicz and Y. Beldjoudi and J.J. Hayward and W.T.K. Chan and E.L. Gavey and M. Pilkington and E. Zysman-Colman and J.M. Rawson",

note = "The authors thank the EPSRC (E.R.C.), NSERC (M.P.; J.M.R.; E.Z.-C.) and the Canada Research Chairs program (M.P.; J.M.R.) for financial support ",

year = "2014",

month = sep,

day = "14",

doi = "10.1039/c4dt01413h",

language = "English",

volume = "43",

pages = "12996--13005",

journal = "Dalton Transactions",

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TY - JOUR

T1 - Synthesis and characterisation of first row transition metal complexes of functionalized 1,2,4-benzothiadiazines

AU - Clark, E.R.

AU - Anwar, M.U.

AU - Leontowicz, B.J.

AU - Beldjoudi, Y.

AU - Hayward, J.J.

AU - Chan, W.T.K.

AU - Gavey, E.L.

AU - Pilkington, M.

AU - Zysman-Colman, E.

AU - Rawson, J.M.

N1 - The authors thank the EPSRC (E.R.C.), NSERC (M.P.; J.M.R.; E.Z.-C.) and the Canada Research Chairs program (M.P.; J.M.R.) for financial support

PY - 2014/9/14

Y1 - 2014/9/14

N2 - Reaction of the novel ligand 3-(2′-pyridyl)-benzo-1,2,4-thiadiazine (L) with the transition metal chloride salts MCl2·xH2O (MII = Mn, Fe, Co, Cu and Zn) in a 2 : 1 mole ratio afforded the mononuclear octahedral (high spin) complexes L2MCl2 (1a–1e respectively) in which L binds in a chelate fashion via N(2) and the pyridyl N atoms. In the case of CuCl2 the intermediate 1 : 1 four-coordinate complex LCuCl2 (2) was also isolated which adopts a polymeric structure with pseudo-square planar molecules linked via long CuS contacts (dCu…S = 2.938(1) Å) in the apical position. In the presence of non-interacting ions, 3 : 1 complexes are isolated, exemplified by the reaction of L with Fe(CF3SO3)2 in a 3 : 1 ratio which affords the low spin complex [L3Fe][CF3SO3]2 (3). Reaction of L with VCl3 in a 2 : 1 mole ratio under aerobic conditions afforded the vanadyl complex [L2V(=O)Cl][Cl] (4).

AB - Reaction of the novel ligand 3-(2′-pyridyl)-benzo-1,2,4-thiadiazine (L) with the transition metal chloride salts MCl2·xH2O (MII = Mn, Fe, Co, Cu and Zn) in a 2 : 1 mole ratio afforded the mononuclear octahedral (high spin) complexes L2MCl2 (1a–1e respectively) in which L binds in a chelate fashion via N(2) and the pyridyl N atoms. In the case of CuCl2 the intermediate 1 : 1 four-coordinate complex LCuCl2 (2) was also isolated which adopts a polymeric structure with pseudo-square planar molecules linked via long CuS contacts (dCu…S = 2.938(1) Å) in the apical position. In the presence of non-interacting ions, 3 : 1 complexes are isolated, exemplified by the reaction of L with Fe(CF3SO3)2 in a 3 : 1 ratio which affords the low spin complex [L3Fe][CF3SO3]2 (3). Reaction of L with VCl3 in a 2 : 1 mole ratio under aerobic conditions afforded the vanadyl complex [L2V(=O)Cl][Cl] (4).

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DO - 10.1039/c4dt01413h

M3 - Article

AN - SCOPUS:84905727811

SN - 1477-9226

VL - 43

SP - 12996

EP - 13005

JO - Dalton Transactions

JF - Dalton Transactions

IS - 34

ER -

Synthesis and characterisation of first row transition metal complexes of functionalized 1,2,4-benzothiadiazines

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