T-Shaped Palladium and Platinum {MNO}10 Nitrosyl Complexes

Matthew J. G. Sinclair; Nil Roig; Matthew R. Gyton; Nikolaos Tsoureas; F. Geoffrey N. Cloke; Mercedes Alonso; Adrian B. Chaplin

doi:10.1021/acs.inorgchem.3c03434

T-Shaped Palladium and Platinum {MNO}10 Nitrosyl Complexes

Matthew J. G. Sinclair, Nil Roig, Matthew R. Gyton, Nikolaos Tsoureas, F. Geoffrey N. Cloke, Mercedes Alonso, Adrian B. Chaplin

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

3 Citations (Scopus)

Abstract

The synthesis and characterization of a homologous series of T-shaped {MNO}10 nitrosyl complexes of the form [M(PR3)2(NO)]+ (M = Pd, Pt; R = tBu, Ad) are reported. These diamagnetic nitrosyls are obtained from monovalent or zerovalent precursors by treatment with NO and NO+, respectively, and are notable for distinctly bent M–NO angles of ∼123° in the solid state. Adoption of this coordination mode in solution is also supported by the analysis of isotopically enriched samples by 15N NMR spectroscopy. Effective oxidation states of M0/NO+ are calculated, and metal–nitrosyl bonding has been interrogated using DFT-based energy decomposition analysis techniques. While a linear nitrosyl coordination mode was found to be electronically preferred, the M–NO and P–M–P angles are inversely correlated to the extent that binding in this manner is prevented by steric repulsion between the bulky ancillary phosphine ligands.

Original language	English
Pages (from-to)	1709-1713
Number of pages	5
Journal	Inorganic Chemistry
Volume	63
Issue number	4
DOIs	https://doi.org/10.1021/acs.inorgchem.3c03434
Publication status	Published - 11 Jan 2024

Bibliographical note

Funding Information:
We gratefully acknowledge funding from the EPSRC (DTP studentship to M.J.G.S.), EUTOPIA alliance (cotutelle studentship to N.R.), European Research Council (grant agreement 637313; M.R.G, A.B.C.), Vrije Universiteit Brussel (M.A.), and Royal Society (UF100592, UF150675; A.B.C). Crystallographic data were collected using an instrument that received funding from the ERC under the European Union’s Horizon 2020 research and innovation programme (grant agreement No. 637313). Tier2 computational resources and services were provided by the Shared ICT Services Centre funded by the VUB, the Flemish Supercomputer Center (VSC) and FWO.

Publisher Copyright:
© 2024 The Authors. Published by American Chemical Society.

Access to Document

10.1021/acs.inorgchem.3c03434

Cite this

@article{b27a3a8f74334cf788e649b418f4a66b,

title = "T-Shaped Palladium and Platinum {MNO}10 Nitrosyl Complexes",

abstract = "The synthesis and characterization of a homologous series of T-shaped {MNO}10 nitrosyl complexes of the form [M(PR3)2(NO)]+ (M = Pd, Pt; R = tBu, Ad) are reported. These diamagnetic nitrosyls are obtained from monovalent or zerovalent precursors by treatment with NO and NO+, respectively, and are notable for distinctly bent M–NO angles of ∼123° in the solid state. Adoption of this coordination mode in solution is also supported by the analysis of isotopically enriched samples by 15N NMR spectroscopy. Effective oxidation states of M0/NO+ are calculated, and metal–nitrosyl bonding has been interrogated using DFT-based energy decomposition analysis techniques. While a linear nitrosyl coordination mode was found to be electronically preferred, the M–NO and P–M–P angles are inversely correlated to the extent that binding in this manner is prevented by steric repulsion between the bulky ancillary phosphine ligands.",

author = "Sinclair, {Matthew J. G.} and Nil Roig and Gyton, {Matthew R.} and Nikolaos Tsoureas and Cloke, {F. Geoffrey N.} and Mercedes Alonso and Chaplin, {Adrian B.}",

note = "Funding Information: We gratefully acknowledge funding from the EPSRC (DTP studentship to M.J.G.S.), EUTOPIA alliance (cotutelle studentship to N.R.), European Research Council (grant agreement 637313; M.R.G, A.B.C.), Vrije Universiteit Brussel (M.A.), and Royal Society (UF100592, UF150675; A.B.C). Crystallographic data were collected using an instrument that received funding from the ERC under the European Union{\textquoteright}s Horizon 2020 research and innovation programme (grant agreement No. 637313). Tier2 computational resources and services were provided by the Shared ICT Services Centre funded by the VUB, the Flemish Supercomputer Center (VSC) and FWO. Publisher Copyright: {\textcopyright} 2024 The Authors. Published by American Chemical Society.",

year = "2024",

month = jan,

day = "11",

doi = "10.1021/acs.inorgchem.3c03434",

language = "English",

volume = "63",

pages = "1709--1713",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "4",

}

TY - JOUR

T1 - T-Shaped Palladium and Platinum {MNO}10 Nitrosyl Complexes

AU - Sinclair, Matthew J. G.

AU - Roig, Nil

AU - Gyton, Matthew R.

AU - Tsoureas, Nikolaos

AU - Cloke, F. Geoffrey N.

AU - Alonso, Mercedes

AU - Chaplin, Adrian B.

N1 - Funding Information: We gratefully acknowledge funding from the EPSRC (DTP studentship to M.J.G.S.), EUTOPIA alliance (cotutelle studentship to N.R.), European Research Council (grant agreement 637313; M.R.G, A.B.C.), Vrije Universiteit Brussel (M.A.), and Royal Society (UF100592, UF150675; A.B.C). Crystallographic data were collected using an instrument that received funding from the ERC under the European Union’s Horizon 2020 research and innovation programme (grant agreement No. 637313). Tier2 computational resources and services were provided by the Shared ICT Services Centre funded by the VUB, the Flemish Supercomputer Center (VSC) and FWO. Publisher Copyright: © 2024 The Authors. Published by American Chemical Society.

PY - 2024/1/11

Y1 - 2024/1/11

N2 - The synthesis and characterization of a homologous series of T-shaped {MNO}10 nitrosyl complexes of the form [M(PR3)2(NO)]+ (M = Pd, Pt; R = tBu, Ad) are reported. These diamagnetic nitrosyls are obtained from monovalent or zerovalent precursors by treatment with NO and NO+, respectively, and are notable for distinctly bent M–NO angles of ∼123° in the solid state. Adoption of this coordination mode in solution is also supported by the analysis of isotopically enriched samples by 15N NMR spectroscopy. Effective oxidation states of M0/NO+ are calculated, and metal–nitrosyl bonding has been interrogated using DFT-based energy decomposition analysis techniques. While a linear nitrosyl coordination mode was found to be electronically preferred, the M–NO and P–M–P angles are inversely correlated to the extent that binding in this manner is prevented by steric repulsion between the bulky ancillary phosphine ligands.

AB - The synthesis and characterization of a homologous series of T-shaped {MNO}10 nitrosyl complexes of the form [M(PR3)2(NO)]+ (M = Pd, Pt; R = tBu, Ad) are reported. These diamagnetic nitrosyls are obtained from monovalent or zerovalent precursors by treatment with NO and NO+, respectively, and are notable for distinctly bent M–NO angles of ∼123° in the solid state. Adoption of this coordination mode in solution is also supported by the analysis of isotopically enriched samples by 15N NMR spectroscopy. Effective oxidation states of M0/NO+ are calculated, and metal–nitrosyl bonding has been interrogated using DFT-based energy decomposition analysis techniques. While a linear nitrosyl coordination mode was found to be electronically preferred, the M–NO and P–M–P angles are inversely correlated to the extent that binding in this manner is prevented by steric repulsion between the bulky ancillary phosphine ligands.

UR - https://doi.org/10.1021/acs.inorgchem.3c03434

UR - http://www.scopus.com/inward/record.url?scp=85182579291&partnerID=8YFLogxK

U2 - 10.1021/acs.inorgchem.3c03434

DO - 10.1021/acs.inorgchem.3c03434

M3 - Article

C2 - 38207212

VL - 63

SP - 1709

EP - 1713

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 4

ER -

T-Shaped Palladium and Platinum {MNO}10 Nitrosyl Complexes

Abstract

Bibliographical note

Access to Document

Other files and links

Fingerprint

Cite this