Alternative syntheses and reactivity of platinum(II) terpyridyl acetonitrile complexes

Ted M. Pappenfus; Jason R. Burney; Kari A. McGee; Garett G.W. Lee; Larissa R. Jarvis; Daniel P. Ekerholm; Mohamed Farah; Lisa I. Smith; Lindsay M. Hinkle; Kent R Mann

doi:10.1016/j.ica.2010.05.060

Alternative syntheses and reactivity of platinum(II) terpyridyl acetonitrile complexes

Ted M. Pappenfus, Jason R. Burney, Kari A. McGee, Garett G.W. Lee, Larissa R. Jarvis, Daniel P. Ekerholm, Mohamed Farah, Lisa I. Smith, Lindsay M. Hinkle, Kent R Mann

Chemistry (Twin Cities)

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

13 Scopus citations

Abstract

New direct syntheses of [Pt(trpy)(NCCH₃)](CF₃SO ₃)₂ 2 (where trpy = 2,2′:6′,2′′- terpyridine) and [Pt(tBu₃-trpy)(NCCH₃)](CF ₃SO₃)₂ 3 (where tBu₃-trpy = 4,4′,4″-tri-tert-butyl-2,2′:6′,2″-terpyridine) via the displacement of acetonitrile from [Pt(NCCH₃)₄] (CF₃SO₃)₂ have been developed. The synthetic utility of 2 was investigated in reactions with triphenylphosphine (PPh ₃), 2,6-dimethylphenyl isocyanide (CN-Xyl), 2,5-dimethyl-2,5- diisocyanohexane (TM4), and tert-butyl isocyanide (CN-tBu). Whereas the expected substitution products were observed for reactions with PPh₃, CN-Xyl, and CN-tBu, dealkylation of TM4 occurred to afford [Pt(trpy)(CN)](CF ₃SO₃) 6. The structures of [Pt(trpy)L]²⁺ dications show little intermolecular interactions in the solid state, with the exception of the tBu₃-trpy complex 3 which exists as head-to-tail dimers with a Pt-Pt distance of 3.29 . The cyano product 6 was found to stack in infinite chains of cations with a Pt-Pt distance of 3.45 .

Original language	English (US)
Pages (from-to)	3214-3221
Number of pages	8
Journal	Inorganica Chimica Acta
Volume	363
Issue number	13
DOIs	https://doi.org/10.1016/j.ica.2010.05.060
State	Published - Oct 25 2010

Bibliographical note

Funding Information:
This research was supported, in part, by the following programs of the National Science Foundation : Research Site for Educators in Chemistry program at the University of Minnesota , Twin Cities ( award #0113894 ); Major Research Instrumentation program ( award #0722669 ); and the Louis Stokes Alliance for Minority Partnership (LSAMP) initiative ( award #0703356 ). T.M.P. acknowledges the following: Dr. Daron Janzen for helpful discussions on the crystallographic data; The Supercomputing Institute of the University of Minnesota; University of Minnesota, Morris (UMM) Faculty Research Enhancement Funds supported by the University of Minnesota Office of the Vice President for Research; and the UMM Division of Science and Mathematics.

Keywords

Platinum complexes
Terpyridine complexes
X-ray crystal structures

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title = "Alternative syntheses and reactivity of platinum(II) terpyridyl acetonitrile complexes",

abstract = "New direct syntheses of [Pt(trpy)(NCCH3)](CF3SO 3)2 2 (where trpy = 2,2′:6′,2′′- terpyridine) and [Pt(tBu3-trpy)(NCCH3)](CF 3SO3)2 3 (where tBu3-trpy = 4,4′,4″-tri-tert-butyl-2,2′:6′,2″-terpyridine) via the displacement of acetonitrile from [Pt(NCCH3)4] (CF3SO3)2 have been developed. The synthetic utility of 2 was investigated in reactions with triphenylphosphine (PPh 3), 2,6-dimethylphenyl isocyanide (CN-Xyl), 2,5-dimethyl-2,5- diisocyanohexane (TM4), and tert-butyl isocyanide (CN-tBu). Whereas the expected substitution products were observed for reactions with PPh3, CN-Xyl, and CN-tBu, dealkylation of TM4 occurred to afford [Pt(trpy)(CN)](CF 3SO3) 6. The structures of [Pt(trpy)L]2+ dications show little intermolecular interactions in the solid state, with the exception of the tBu3-trpy complex 3 which exists as head-to-tail dimers with a Pt-Pt distance of 3.29 . The cyano product 6 was found to stack in infinite chains of cations with a Pt-Pt distance of 3.45 .",

keywords = "Platinum complexes, Terpyridine complexes, X-ray crystal structures",

author = "Pappenfus, {Ted M.} and Burney, {Jason R.} and McGee, {Kari A.} and Lee, {Garett G.W.} and Jarvis, {Larissa R.} and Ekerholm, {Daniel P.} and Mohamed Farah and Smith, {Lisa I.} and Hinkle, {Lindsay M.} and Mann, {Kent R}",

note = "Funding Information: This research was supported, in part, by the following programs of the National Science Foundation : Research Site for Educators in Chemistry program at the University of Minnesota , Twin Cities ( award #0113894 ); Major Research Instrumentation program ( award #0722669 ); and the Louis Stokes Alliance for Minority Partnership (LSAMP) initiative ( award #0703356 ). T.M.P. acknowledges the following: Dr. Daron Janzen for helpful discussions on the crystallographic data; The Supercomputing Institute of the University of Minnesota; University of Minnesota, Morris (UMM) Faculty Research Enhancement Funds supported by the University of Minnesota Office of the Vice President for Research; and the UMM Division of Science and Mathematics. ",

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AU - Pappenfus, Ted M.

AU - Burney, Jason R.

AU - McGee, Kari A.

AU - Lee, Garett G.W.

AU - Jarvis, Larissa R.

AU - Ekerholm, Daniel P.

AU - Farah, Mohamed

AU - Smith, Lisa I.

AU - Hinkle, Lindsay M.

AU - Mann, Kent R

N1 - Funding Information: This research was supported, in part, by the following programs of the National Science Foundation : Research Site for Educators in Chemistry program at the University of Minnesota , Twin Cities ( award #0113894 ); Major Research Instrumentation program ( award #0722669 ); and the Louis Stokes Alliance for Minority Partnership (LSAMP) initiative ( award #0703356 ). T.M.P. acknowledges the following: Dr. Daron Janzen for helpful discussions on the crystallographic data; The Supercomputing Institute of the University of Minnesota; University of Minnesota, Morris (UMM) Faculty Research Enhancement Funds supported by the University of Minnesota Office of the Vice President for Research; and the UMM Division of Science and Mathematics.

PY - 2010/10/25

Y1 - 2010/10/25

N2 - New direct syntheses of [Pt(trpy)(NCCH3)](CF3SO 3)2 2 (where trpy = 2,2′:6′,2′′- terpyridine) and [Pt(tBu3-trpy)(NCCH3)](CF 3SO3)2 3 (where tBu3-trpy = 4,4′,4″-tri-tert-butyl-2,2′:6′,2″-terpyridine) via the displacement of acetonitrile from [Pt(NCCH3)4] (CF3SO3)2 have been developed. The synthetic utility of 2 was investigated in reactions with triphenylphosphine (PPh 3), 2,6-dimethylphenyl isocyanide (CN-Xyl), 2,5-dimethyl-2,5- diisocyanohexane (TM4), and tert-butyl isocyanide (CN-tBu). Whereas the expected substitution products were observed for reactions with PPh3, CN-Xyl, and CN-tBu, dealkylation of TM4 occurred to afford [Pt(trpy)(CN)](CF 3SO3) 6. The structures of [Pt(trpy)L]2+ dications show little intermolecular interactions in the solid state, with the exception of the tBu3-trpy complex 3 which exists as head-to-tail dimers with a Pt-Pt distance of 3.29 . The cyano product 6 was found to stack in infinite chains of cations with a Pt-Pt distance of 3.45 .

AB - New direct syntheses of [Pt(trpy)(NCCH3)](CF3SO 3)2 2 (where trpy = 2,2′:6′,2′′- terpyridine) and [Pt(tBu3-trpy)(NCCH3)](CF 3SO3)2 3 (where tBu3-trpy = 4,4′,4″-tri-tert-butyl-2,2′:6′,2″-terpyridine) via the displacement of acetonitrile from [Pt(NCCH3)4] (CF3SO3)2 have been developed. The synthetic utility of 2 was investigated in reactions with triphenylphosphine (PPh 3), 2,6-dimethylphenyl isocyanide (CN-Xyl), 2,5-dimethyl-2,5- diisocyanohexane (TM4), and tert-butyl isocyanide (CN-tBu). Whereas the expected substitution products were observed for reactions with PPh3, CN-Xyl, and CN-tBu, dealkylation of TM4 occurred to afford [Pt(trpy)(CN)](CF 3SO3) 6. The structures of [Pt(trpy)L]2+ dications show little intermolecular interactions in the solid state, with the exception of the tBu3-trpy complex 3 which exists as head-to-tail dimers with a Pt-Pt distance of 3.29 . The cyano product 6 was found to stack in infinite chains of cations with a Pt-Pt distance of 3.45 .

KW - Platinum complexes

KW - Terpyridine complexes

KW - X-ray crystal structures

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Alternative syntheses and reactivity of platinum(II) terpyridyl acetonitrile complexes

Abstract

Bibliographical note

Keywords

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