Supramolecular assemblies of dimetal complexes with polydentate N-donor ligands: From a discrete pyramid to a 3D channel network

F. Albert Cotton; Evgeny V. Dikarev; Marina A. Petrukhina; Marion Schmitz; Peter J. Stang

doi:10.1021/ic020051s

Supramolecular assemblies of dimetal complexes with polydentate N-donor ligands: From a discrete pyramid to a 3D channel network

F. Albert Cotton
, Evgeny V. Dikarev
, Marina A. Petrukhina
, Marion Schmitz
, Peter J. Stang

Chemistry

University at Albany

Texas A&M University
University of Utah

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

49 Scopus citations

Abstract

Reactions of a dinuclear metal complex in the form of dirhodium(II) tetra(trifluoroacetate), [Rh₂(O₂CCF₃)₄] (1), with a number of strong N-donor ligands having functional groups rigidly oriented at different directing angles have been found to yield supramolecular architectures of differing complexity. All structures have been established by X-ray crystallography. From reaction of 1 with neutral tris(4′-pyridyl)methylsilane ligand, CH₃Si(C₅H₄N)₃ (L1), a discrete pyramid-shaped hexanuclear complex {[Rh₂(O₂CCF₃)₄]₃ CH₃Si(C₅H₄N)₃ (η¹-C₆H₆)₃} ·C₆H₆ (2·C₆H₆) has been isolated from benzene. In 2 three molecules of 1 are strongly coordinated to one L1 ligand at only one axial position of each dirhodium unit at the Rh-N distances of 2.152(6) Å. The second rhodium atom of each dimetal complex in 2 weakly coordinates a benzene molecule with an Rh-C distance of 2.69(2) Å. A supramolecular complex of the composition {[Rh₂(O₂CCF₃)₄]₂ (C₆H₅)₂Si (C₅H₄N)₂} (3) has been prepared by reacting the dinuclear units 1 with a potentially bidentate ligand, bis(4′-pyridyl)diphenylsilane, (C₆H₅)₂Si (C₅H₄N)₂ (L2), having two pyridyl groups rigidly oriented at 109°. In 3, one L2 ligand coordinates two dirhodium molecules 1 through their axial positions with the Rh-N distance of 2.150(5) Å. An interesting extended 2D layered motif is formed by additional contacts of open axial positions of dirhodium units with phenyl groups of the neighboring ligands at Rh-C distances which average to 2.88(1) Å. A supramolecular compound of the composition {[Rh₂(O₂CCF₃)₄]₃ (HO)C(C₅H₄N)₃ (η¹-C₆H₆)}·1/2C₆ H₆ (4·1/2C₆H₆) has been formed when linear dirhodium units 1 were reacted with tris(4′-pyridyl) methanol (L3) having tetrahedral directing angles that average to 110°. A building block in the solid structure of 4 is a hexanuclear molecule in which one L3 ligand binds three dimetal units of 1 through N atoms of pyridyl groups at the average Rh-N distance of 2.143(7) Å. A unique extended pseudo-3D structure in 4 is created by additional Rh-O coordination bonds as well as by weak metal-arene interactions.

Original language	English
Pages (from-to)	2903-2908
Number of pages	6
Journal	Inorganic Chemistry
Volume	41
Issue number	11
DOIs	https://doi.org/10.1021/ic020051s
State	Published - Jun 3 2002

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10.1021/ic020051s

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@article{76b01b92824144f1b349c2aedcc96cad,

title = "Supramolecular assemblies of dimetal complexes with polydentate N-donor ligands: From a discrete pyramid to a 3D channel network",

abstract = "Reactions of a dinuclear metal complex in the form of dirhodium(II) tetra(trifluoroacetate), [Rh2(O2CCF3)4] (1), with a number of strong N-donor ligands having functional groups rigidly oriented at different directing angles have been found to yield supramolecular architectures of differing complexity. All structures have been established by X-ray crystallography. From reaction of 1 with neutral tris(4′-pyridyl)methylsilane ligand, CH3Si(C5H4N)3 (L1), a discrete pyramid-shaped hexanuclear complex \{[Rh2(O2CCF3)4]3 CH3Si(C5H4N)3 (η1-C6H6)3\} ·C6H6 (2·C6H6) has been isolated from benzene. In 2 three molecules of 1 are strongly coordinated to one L1 ligand at only one axial position of each dirhodium unit at the Rh-N distances of 2.152(6) {\AA}. The second rhodium atom of each dimetal complex in 2 weakly coordinates a benzene molecule with an Rh-C distance of 2.69(2) {\AA}. A supramolecular complex of the composition \{[Rh2(O2CCF3)4]2 (C6H5)2Si (C5H4N)2\} (3) has been prepared by reacting the dinuclear units 1 with a potentially bidentate ligand, bis(4′-pyridyl)diphenylsilane, (C6H5)2Si (C5H4N)2 (L2), having two pyridyl groups rigidly oriented at 109°. In 3, one L2 ligand coordinates two dirhodium molecules 1 through their axial positions with the Rh-N distance of 2.150(5) {\AA}. An interesting extended 2D layered motif is formed by additional contacts of open axial positions of dirhodium units with phenyl groups of the neighboring ligands at Rh-C distances which average to 2.88(1) {\AA}. A supramolecular compound of the composition \{[Rh2(O2CCF3)4]3 (HO)C(C5H4N)3 (η1-C6H6)\}·1/2C6 H6 (4·1/2C6H6) has been formed when linear dirhodium units 1 were reacted with tris(4′-pyridyl) methanol (L3) having tetrahedral directing angles that average to 110°. A building block in the solid structure of 4 is a hexanuclear molecule in which one L3 ligand binds three dimetal units of 1 through N atoms of pyridyl groups at the average Rh-N distance of 2.143(7) {\AA}. A unique extended pseudo-3D structure in 4 is created by additional Rh-O coordination bonds as well as by weak metal-arene interactions.",

author = "Cotton, \{F. Albert\} and Dikarev, \{Evgeny V.\} and Petrukhina, \{Marina A.\} and Marion Schmitz and Stang, \{Peter J.\}",

year = "2002",

month = jun,

day = "3",

doi = "10.1021/ic020051s",

language = "English",

volume = "41",

pages = "2903--2908",

journal = "Inorganic Chemistry",

issn = "0020-1669",

number = "11",

}

TY - JOUR

T1 - Supramolecular assemblies of dimetal complexes with polydentate N-donor ligands

T2 - From a discrete pyramid to a 3D channel network

AU - Cotton, F. Albert

AU - Dikarev, Evgeny V.

AU - Petrukhina, Marina A.

AU - Schmitz, Marion

AU - Stang, Peter J.

PY - 2002/6/3

Y1 - 2002/6/3

N2 - Reactions of a dinuclear metal complex in the form of dirhodium(II) tetra(trifluoroacetate), [Rh2(O2CCF3)4] (1), with a number of strong N-donor ligands having functional groups rigidly oriented at different directing angles have been found to yield supramolecular architectures of differing complexity. All structures have been established by X-ray crystallography. From reaction of 1 with neutral tris(4′-pyridyl)methylsilane ligand, CH3Si(C5H4N)3 (L1), a discrete pyramid-shaped hexanuclear complex {[Rh2(O2CCF3)4]3 CH3Si(C5H4N)3 (η1-C6H6)3} ·C6H6 (2·C6H6) has been isolated from benzene. In 2 three molecules of 1 are strongly coordinated to one L1 ligand at only one axial position of each dirhodium unit at the Rh-N distances of 2.152(6) Å. The second rhodium atom of each dimetal complex in 2 weakly coordinates a benzene molecule with an Rh-C distance of 2.69(2) Å. A supramolecular complex of the composition {[Rh2(O2CCF3)4]2 (C6H5)2Si (C5H4N)2} (3) has been prepared by reacting the dinuclear units 1 with a potentially bidentate ligand, bis(4′-pyridyl)diphenylsilane, (C6H5)2Si (C5H4N)2 (L2), having two pyridyl groups rigidly oriented at 109°. In 3, one L2 ligand coordinates two dirhodium molecules 1 through their axial positions with the Rh-N distance of 2.150(5) Å. An interesting extended 2D layered motif is formed by additional contacts of open axial positions of dirhodium units with phenyl groups of the neighboring ligands at Rh-C distances which average to 2.88(1) Å. A supramolecular compound of the composition {[Rh2(O2CCF3)4]3 (HO)C(C5H4N)3 (η1-C6H6)}·1/2C6 H6 (4·1/2C6H6) has been formed when linear dirhodium units 1 were reacted with tris(4′-pyridyl) methanol (L3) having tetrahedral directing angles that average to 110°. A building block in the solid structure of 4 is a hexanuclear molecule in which one L3 ligand binds three dimetal units of 1 through N atoms of pyridyl groups at the average Rh-N distance of 2.143(7) Å. A unique extended pseudo-3D structure in 4 is created by additional Rh-O coordination bonds as well as by weak metal-arene interactions.

AB - Reactions of a dinuclear metal complex in the form of dirhodium(II) tetra(trifluoroacetate), [Rh2(O2CCF3)4] (1), with a number of strong N-donor ligands having functional groups rigidly oriented at different directing angles have been found to yield supramolecular architectures of differing complexity. All structures have been established by X-ray crystallography. From reaction of 1 with neutral tris(4′-pyridyl)methylsilane ligand, CH3Si(C5H4N)3 (L1), a discrete pyramid-shaped hexanuclear complex {[Rh2(O2CCF3)4]3 CH3Si(C5H4N)3 (η1-C6H6)3} ·C6H6 (2·C6H6) has been isolated from benzene. In 2 three molecules of 1 are strongly coordinated to one L1 ligand at only one axial position of each dirhodium unit at the Rh-N distances of 2.152(6) Å. The second rhodium atom of each dimetal complex in 2 weakly coordinates a benzene molecule with an Rh-C distance of 2.69(2) Å. A supramolecular complex of the composition {[Rh2(O2CCF3)4]2 (C6H5)2Si (C5H4N)2} (3) has been prepared by reacting the dinuclear units 1 with a potentially bidentate ligand, bis(4′-pyridyl)diphenylsilane, (C6H5)2Si (C5H4N)2 (L2), having two pyridyl groups rigidly oriented at 109°. In 3, one L2 ligand coordinates two dirhodium molecules 1 through their axial positions with the Rh-N distance of 2.150(5) Å. An interesting extended 2D layered motif is formed by additional contacts of open axial positions of dirhodium units with phenyl groups of the neighboring ligands at Rh-C distances which average to 2.88(1) Å. A supramolecular compound of the composition {[Rh2(O2CCF3)4]3 (HO)C(C5H4N)3 (η1-C6H6)}·1/2C6 H6 (4·1/2C6H6) has been formed when linear dirhodium units 1 were reacted with tris(4′-pyridyl) methanol (L3) having tetrahedral directing angles that average to 110°. A building block in the solid structure of 4 is a hexanuclear molecule in which one L3 ligand binds three dimetal units of 1 through N atoms of pyridyl groups at the average Rh-N distance of 2.143(7) Å. A unique extended pseudo-3D structure in 4 is created by additional Rh-O coordination bonds as well as by weak metal-arene interactions.

UR - https://www.scopus.com/pages/publications/0037013792

U2 - 10.1021/ic020051s

DO - 10.1021/ic020051s

M3 - Article

C2 - 12033898

SN - 0020-1669

VL - 41

SP - 2903

EP - 2908

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 11

ER -

Supramolecular assemblies of dimetal complexes with polydentate N-donor ligands: From a discrete pyramid to a 3D channel network

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