Synthesis, characterization, and electrochemical relationships of dinuclear complexes of platinum(II) and platinum(III) containing ortho-metalated tertiary arsine ligands

Martin A. Bennett; Suresh K. Bhargava; Alan M. Bond; Alison J. Edwards; Si Xuan Guo; Steven H. Privér; A. David Rae; Anthony C. Willis

doi:10.1021/ic0498790

Synthesis, characterization, and electrochemical relationships of dinuclear complexes of platinum(II) and platinum(III) containing ortho-metalated tertiary arsine ligands

Martin A. Bennett, Suresh K. Bhargava^*, Alan M. Bond, Alison J. Edwards, Si Xuan Guo, Steven H. Privér, A. David Rae, Anthony C. Willis

^*Corresponding author for this work

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

33 Citations (Scopus)

Abstract

Reaction of 2-Li-4-MeC₆H₃AsPh₂ with [PtCl₂(SEt₂)₂] gives two isomeric dinuclear platinum(II) complexes, one containing a half-lantern structure with two chelating and two bridging C₆H₃-5-Me-2-AsPh₂ ligands, [Pt₂(κ²As,C-C₆H ₃-5-Me-2-AsPh₂)₂(μ-κAs,κC-C ₆H₃-5-Me-2-AsPh₂)₂], and the other, a full-lantern with four bridging C₆H₃-5-Me-2-AsPh ₂ ligands, [Pt₂(μ-κAs,κC-C ₆H₃-5-Me-2-AsPh₂)₄]. The lantern structure of the latter is retained in the dihalodiplatinum(III) complexes that are formed by oxidative addition of chlorine, bromine, or iodine to the isomeric mixture. The dichloro derivative undergoes metathesis reactions with silver or sodium salts, yielding the corresponding cyano, thiocyanato, cyanato, and fluoro species. The structures of all complexes have been determined by single-crystal X-ray analysis. The oxidative addition products have Pt-Pt distances in the range 2.65-279 Å (cf. 2.89 Å in the lantern diplatinum(II) structure), consistent with the presence of a Pt-Pt bond. Electrochemical data lead to the conclusion that an initial rapid one-electron process and subsequent chemical reactions produce the dihalodiplatinum(III) lantern structure when mixtures of the lantern and half-lantern complexes are oxidized by halogens. The electrochemical data also explain why chemical reduction of the dihalodiplatinum(III) complex produces only the lantern diplatinum(II) complex.

Original language	English
Pages (from-to)	7752-7763
Number of pages	12
Journal	Inorganic Chemistry
Volume	43
Issue number	24
DOIs	https://doi.org/10.1021/ic0498790
Publication status	Published - 29 Nov 2004

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Bennett, M. A., Bhargava, S. K., Bond, A. M., Edwards, A. J., Guo, S. X., Privér, S. H., Rae, A. D., & Willis, A. C. (2004). Synthesis, characterization, and electrochemical relationships of dinuclear complexes of platinum(II) and platinum(III) containing ortho-metalated tertiary arsine ligands. Inorganic Chemistry, 43(24), 7752-7763. https://doi.org/10.1021/ic0498790

@article{9560b4726340499ea224f2a88e34e196,

title = "Synthesis, characterization, and electrochemical relationships of dinuclear complexes of platinum(II) and platinum(III) containing ortho-metalated tertiary arsine ligands",

abstract = "Reaction of 2-Li-4-MeC6H3AsPh2 with [PtCl2(SEt2)2] gives two isomeric dinuclear platinum(II) complexes, one containing a half-lantern structure with two chelating and two bridging C6H3-5-Me-2-AsPh2 ligands, [Pt2(κ2As,C-C6H 3-5-Me-2-AsPh2)2(μ-κAs,κC-C 6H3-5-Me-2-AsPh2)2], and the other, a full-lantern with four bridging C6H3-5-Me-2-AsPh 2 ligands, [Pt2(μ-κAs,κC-C 6H3-5-Me-2-AsPh2)4]. The lantern structure of the latter is retained in the dihalodiplatinum(III) complexes that are formed by oxidative addition of chlorine, bromine, or iodine to the isomeric mixture. The dichloro derivative undergoes metathesis reactions with silver or sodium salts, yielding the corresponding cyano, thiocyanato, cyanato, and fluoro species. The structures of all complexes have been determined by single-crystal X-ray analysis. The oxidative addition products have Pt-Pt distances in the range 2.65-279 {\AA} (cf. 2.89 {\AA} in the lantern diplatinum(II) structure), consistent with the presence of a Pt-Pt bond. Electrochemical data lead to the conclusion that an initial rapid one-electron process and subsequent chemical reactions produce the dihalodiplatinum(III) lantern structure when mixtures of the lantern and half-lantern complexes are oxidized by halogens. The electrochemical data also explain why chemical reduction of the dihalodiplatinum(III) complex produces only the lantern diplatinum(II) complex.",

author = "Bennett, {Martin A.} and Bhargava, {Suresh K.} and Bond, {Alan M.} and Edwards, {Alison J.} and Guo, {Si Xuan} and Priv{\'e}r, {Steven H.} and Rae, {A. David} and Willis, {Anthony C.}",

year = "2004",

month = nov,

day = "29",

doi = "10.1021/ic0498790",

language = "English",

volume = "43",

pages = "7752--7763",

journal = "Inorganic Chemistry",

issn = "0020-1669",

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Synthesis, characterization, and electrochemical relationships of dinuclear complexes of platinum(II) and platinum(III) containing ortho-metalated tertiary arsine ligands. / Bennett, Martin A.; Bhargava, Suresh K.; Bond, Alan M. et al.
In: Inorganic Chemistry, Vol. 43, No. 24, 29.11.2004, p. 7752-7763.

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

TY - JOUR

T1 - Synthesis, characterization, and electrochemical relationships of dinuclear complexes of platinum(II) and platinum(III) containing ortho-metalated tertiary arsine ligands

AU - Bennett, Martin A.

AU - Bhargava, Suresh K.

AU - Bond, Alan M.

AU - Edwards, Alison J.

AU - Guo, Si Xuan

AU - Privér, Steven H.

AU - Rae, A. David

AU - Willis, Anthony C.

PY - 2004/11/29

Y1 - 2004/11/29

N2 - Reaction of 2-Li-4-MeC6H3AsPh2 with [PtCl2(SEt2)2] gives two isomeric dinuclear platinum(II) complexes, one containing a half-lantern structure with two chelating and two bridging C6H3-5-Me-2-AsPh2 ligands, [Pt2(κ2As,C-C6H 3-5-Me-2-AsPh2)2(μ-κAs,κC-C 6H3-5-Me-2-AsPh2)2], and the other, a full-lantern with four bridging C6H3-5-Me-2-AsPh 2 ligands, [Pt2(μ-κAs,κC-C 6H3-5-Me-2-AsPh2)4]. The lantern structure of the latter is retained in the dihalodiplatinum(III) complexes that are formed by oxidative addition of chlorine, bromine, or iodine to the isomeric mixture. The dichloro derivative undergoes metathesis reactions with silver or sodium salts, yielding the corresponding cyano, thiocyanato, cyanato, and fluoro species. The structures of all complexes have been determined by single-crystal X-ray analysis. The oxidative addition products have Pt-Pt distances in the range 2.65-279 Å (cf. 2.89 Å in the lantern diplatinum(II) structure), consistent with the presence of a Pt-Pt bond. Electrochemical data lead to the conclusion that an initial rapid one-electron process and subsequent chemical reactions produce the dihalodiplatinum(III) lantern structure when mixtures of the lantern and half-lantern complexes are oxidized by halogens. The electrochemical data also explain why chemical reduction of the dihalodiplatinum(III) complex produces only the lantern diplatinum(II) complex.

AB - Reaction of 2-Li-4-MeC6H3AsPh2 with [PtCl2(SEt2)2] gives two isomeric dinuclear platinum(II) complexes, one containing a half-lantern structure with two chelating and two bridging C6H3-5-Me-2-AsPh2 ligands, [Pt2(κ2As,C-C6H 3-5-Me-2-AsPh2)2(μ-κAs,κC-C 6H3-5-Me-2-AsPh2)2], and the other, a full-lantern with four bridging C6H3-5-Me-2-AsPh 2 ligands, [Pt2(μ-κAs,κC-C 6H3-5-Me-2-AsPh2)4]. The lantern structure of the latter is retained in the dihalodiplatinum(III) complexes that are formed by oxidative addition of chlorine, bromine, or iodine to the isomeric mixture. The dichloro derivative undergoes metathesis reactions with silver or sodium salts, yielding the corresponding cyano, thiocyanato, cyanato, and fluoro species. The structures of all complexes have been determined by single-crystal X-ray analysis. The oxidative addition products have Pt-Pt distances in the range 2.65-279 Å (cf. 2.89 Å in the lantern diplatinum(II) structure), consistent with the presence of a Pt-Pt bond. Electrochemical data lead to the conclusion that an initial rapid one-electron process and subsequent chemical reactions produce the dihalodiplatinum(III) lantern structure when mixtures of the lantern and half-lantern complexes are oxidized by halogens. The electrochemical data also explain why chemical reduction of the dihalodiplatinum(III) complex produces only the lantern diplatinum(II) complex.

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U2 - 10.1021/ic0498790

DO - 10.1021/ic0498790

M3 - Article

SN - 0020-1669

VL - 43

SP - 7752

EP - 7763

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 24

ER -

Synthesis, characterization, and electrochemical relationships of dinuclear complexes of platinum(II) and platinum(III) containing ortho-metalated tertiary arsine ligands

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