Platinum(II) phosphine complexes of dicarboxylates and ammonia: Crystal structures of

Andrew D. Burrows; D. Michael P. Mingos; Simon E. Lawrence; Andrew J.P. White; David J. Williams

doi:10.1039/A607909A

Platinum(II) phosphine complexes of dicarboxylates and ammonia: Crystal structures of

Andrew D. Burrows
, D. Michael P. Mingos
, Simon E. Lawrence
, Andrew J.P. White
, David J. Williams

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

Abstract

The reaction of [Pt(PPh₃)₂(CO₃)] with a rigid dicarboxylic acid H₂L gave rise to dimeric compounds [{Pt(PPh₃)₂}₂(μ-L)₂] 1 [H₂L = C₆H₄(CO₂H)₂-1,4 (terephthalic acid) a, C₆H₄(CO₂H)₂-I1S (isophthalic acid) b, trans,trans-HO₂CCH=CHCH=CHCO₂H (muconic acid) c or 4,4′-HO₂CC₆H₄C₆H ₄CO₂H (biphenyldicarboxylic acid) d], which have been characterised spectroscopically and, in the case of 1b, crystallographically. When the reaction was carried out in the presence of NH₄PF₆ the NH₄⁺ competed with the carboxylic acid and the major product from the reaction was [{Pt(PPh₃)₂(NH₃)}₂(μ-L)][PF ₆]₂ 2, which has been characterised crystallographically for L = terephthalate. This suggests that NH₄⁺ is acidic enough to react with [Pt(PPh₃)²(CO₃)], which has been confirmed by the synthesis of cis-[PtL₂(NH₃)₂]X₂ [L = PPh₃, X = PF₆ 3a or NO₃ 3b; L = PEt₃, X = PF₆ 4a or NO₃ 4b; L₂ = Ph₂PCH₂CH₂PPh₂ (dppe), X = PF₆ 5a] from [PtL₂(CO₃)]. The complex cis-[Pt(PPh₃)₂(¹⁵NH₃) ₂][NO₃]₂ was synthesized from ¹⁵NH₄NO₃ and characterised by a combination of ¹¹P-{¹H}, ¹⁵N-{¹H}, ¹⁹⁵Pt and ¹H NMR spectroscopy. The crystal structure of cis-[Pt(PPh₃)₂(NH₃)₂][NO ₃]₂ 3b has been determined and shows strong hydrogen bonding between the co-ordinated ammonia and the nitrate counter ions. The compound PhC₂CO₂H also reacted with [PtL₂(CO₃)], though the products were not the expected bifunctional carboxylates cis-[PtL₂(O₂CC₂Ph)₂] but the bis(phenylalkynyl) compounds cis-[PtL₂(C₂Ph)₂] (L = PPh₃ 6, L₂ = dppe 7).

Original language	English
Pages (from-to)	1295-1300
Number of pages	6
Journal	Journal of the Chemical Society. Dalton Transactions
Issue number	8
DOIs	https://doi.org/10.1039/A607909A
Publication status	Published - 21 Apr 1997
Externally published	Yes

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@article{9be83ed56074462bb0935d7eae879295,

title = "Platinum(II) phosphine complexes of dicarboxylates and ammonia: Crystal structures of",

abstract = "The reaction of [Pt(PPh3)2(CO3)] with a rigid dicarboxylic acid H2L gave rise to dimeric compounds [\{Pt(PPh3)2\}2(μ-L)2] 1 [H2L = C6H4(CO2H)2-1,4 (terephthalic acid) a, C6H4(CO2H)2-I1S (isophthalic acid) b, trans,trans-HO2CCH=CHCH=CHCO2H (muconic acid) c or 4,4′-HO2CC6H4C6H 4CO2H (biphenyldicarboxylic acid) d], which have been characterised spectroscopically and, in the case of 1b, crystallographically. When the reaction was carried out in the presence of NH4PF6 the NH4+ competed with the carboxylic acid and the major product from the reaction was [\{Pt(PPh3)2(NH3)\}2(μ-L)][PF 6]2 2, which has been characterised crystallographically for L = terephthalate. This suggests that NH4+ is acidic enough to react with [Pt(PPh3)2(CO3)], which has been confirmed by the synthesis of cis-[PtL2(NH3)2]X2 [L = PPh3, X = PF6 3a or NO3 3b; L = PEt3, X = PF6 4a or NO3 4b; L2 = Ph2PCH2CH2PPh2 (dppe), X = PF6 5a] from [PtL2(CO3)]. The complex cis-[Pt(PPh3)2(15NH3) 2][NO3]2 was synthesized from 15NH4NO3 and characterised by a combination of 11P-\{1H\}, 15N-\{1H\}, 195Pt and 1H NMR spectroscopy. The crystal structure of cis-[Pt(PPh3)2(NH3)2][NO 3]2 3b has been determined and shows strong hydrogen bonding between the co-ordinated ammonia and the nitrate counter ions. The compound PhC2CO2H also reacted with [PtL2(CO3)], though the products were not the expected bifunctional carboxylates cis-[PtL2(O2CC2Ph)2] but the bis(phenylalkynyl) compounds cis-[PtL2(C2Ph)2] (L = PPh3 6, L2 = dppe 7).",

author = "Burrows, \{Andrew D.\} and Mingos, \{D. Michael P.\} and Lawrence, \{Simon E.\} and White, \{Andrew J.P.\} and Williams, \{David J.\}",

year = "1997",

month = apr,

day = "21",

doi = "10.1039/A607909A",

language = "English",

pages = "1295--1300",

journal = "Journal of the Chemical Society. Dalton Transactions",

issn = "1470-479X",

publisher = "Royal Society of Chemistry",

number = "8",

}

TY - JOUR

T1 - Platinum(II) phosphine complexes of dicarboxylates and ammonia

T2 - Crystal structures of

AU - Burrows, Andrew D.

AU - Mingos, D. Michael P.

AU - Lawrence, Simon E.

AU - White, Andrew J.P.

AU - Williams, David J.

PY - 1997/4/21

Y1 - 1997/4/21

N2 - The reaction of [Pt(PPh3)2(CO3)] with a rigid dicarboxylic acid H2L gave rise to dimeric compounds [{Pt(PPh3)2}2(μ-L)2] 1 [H2L = C6H4(CO2H)2-1,4 (terephthalic acid) a, C6H4(CO2H)2-I1S (isophthalic acid) b, trans,trans-HO2CCH=CHCH=CHCO2H (muconic acid) c or 4,4′-HO2CC6H4C6H 4CO2H (biphenyldicarboxylic acid) d], which have been characterised spectroscopically and, in the case of 1b, crystallographically. When the reaction was carried out in the presence of NH4PF6 the NH4+ competed with the carboxylic acid and the major product from the reaction was [{Pt(PPh3)2(NH3)}2(μ-L)][PF 6]2 2, which has been characterised crystallographically for L = terephthalate. This suggests that NH4+ is acidic enough to react with [Pt(PPh3)2(CO3)], which has been confirmed by the synthesis of cis-[PtL2(NH3)2]X2 [L = PPh3, X = PF6 3a or NO3 3b; L = PEt3, X = PF6 4a or NO3 4b; L2 = Ph2PCH2CH2PPh2 (dppe), X = PF6 5a] from [PtL2(CO3)]. The complex cis-[Pt(PPh3)2(15NH3) 2][NO3]2 was synthesized from 15NH4NO3 and characterised by a combination of 11P-{1H}, 15N-{1H}, 195Pt and 1H NMR spectroscopy. The crystal structure of cis-[Pt(PPh3)2(NH3)2][NO 3]2 3b has been determined and shows strong hydrogen bonding between the co-ordinated ammonia and the nitrate counter ions. The compound PhC2CO2H also reacted with [PtL2(CO3)], though the products were not the expected bifunctional carboxylates cis-[PtL2(O2CC2Ph)2] but the bis(phenylalkynyl) compounds cis-[PtL2(C2Ph)2] (L = PPh3 6, L2 = dppe 7).

AB - The reaction of [Pt(PPh3)2(CO3)] with a rigid dicarboxylic acid H2L gave rise to dimeric compounds [{Pt(PPh3)2}2(μ-L)2] 1 [H2L = C6H4(CO2H)2-1,4 (terephthalic acid) a, C6H4(CO2H)2-I1S (isophthalic acid) b, trans,trans-HO2CCH=CHCH=CHCO2H (muconic acid) c or 4,4′-HO2CC6H4C6H 4CO2H (biphenyldicarboxylic acid) d], which have been characterised spectroscopically and, in the case of 1b, crystallographically. When the reaction was carried out in the presence of NH4PF6 the NH4+ competed with the carboxylic acid and the major product from the reaction was [{Pt(PPh3)2(NH3)}2(μ-L)][PF 6]2 2, which has been characterised crystallographically for L = terephthalate. This suggests that NH4+ is acidic enough to react with [Pt(PPh3)2(CO3)], which has been confirmed by the synthesis of cis-[PtL2(NH3)2]X2 [L = PPh3, X = PF6 3a or NO3 3b; L = PEt3, X = PF6 4a or NO3 4b; L2 = Ph2PCH2CH2PPh2 (dppe), X = PF6 5a] from [PtL2(CO3)]. The complex cis-[Pt(PPh3)2(15NH3) 2][NO3]2 was synthesized from 15NH4NO3 and characterised by a combination of 11P-{1H}, 15N-{1H}, 195Pt and 1H NMR spectroscopy. The crystal structure of cis-[Pt(PPh3)2(NH3)2][NO 3]2 3b has been determined and shows strong hydrogen bonding between the co-ordinated ammonia and the nitrate counter ions. The compound PhC2CO2H also reacted with [PtL2(CO3)], though the products were not the expected bifunctional carboxylates cis-[PtL2(O2CC2Ph)2] but the bis(phenylalkynyl) compounds cis-[PtL2(C2Ph)2] (L = PPh3 6, L2 = dppe 7).

UR - https://www.scopus.com/pages/publications/33748716073

U2 - 10.1039/A607909A

DO - 10.1039/A607909A

M3 - Article

AN - SCOPUS:33748716073

SN - 1470-479X

SP - 1295

EP - 1300

JO - Journal of the Chemical Society. Dalton Transactions

JF - Journal of the Chemical Society. Dalton Transactions

IS - 8

ER -

Platinum(II) phosphine complexes of dicarboxylates and ammonia: Crystal structures of

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