Crystal structures of organometallic aqua complexes [Cp*Rh III(bpy)(OH2)]2+ and [Cp*Rh III(6,6′-Me2bpy)(OH2)]2+ used as key catalysts in regioselective reduction of NAD+ analogues

Seiji Ogo; Hideki Hayashi; Keiji Uehara; Shunichi Fukuzumi

doi:10.1002/aoc.837

Crystal structures of organometallic aqua complexes [CpRh ^III(bpy)(OH₂)]²⁺ and [CpRh ^III(6,6′-Me₂bpy)(OH₂)]²⁺ used as key catalysts in regioselective reduction of NAD⁺ analogues

Seiji Ogo, Hideki Hayashi, Keiji Uehara, Shunichi Fukuzumi

Department of Chemistry & Nanoscience

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

16 Scopus citations

Abstract

Crystal structures of organometallic aqua complexes [Cp*Rh ^III(bpy)(OH₂)]²⁺ (1, Cp* = η ⁵-C₅Me₅, bpy = 2,2′-bipyridine) and [Cp*Rh^III(6,6′-Me₂bpy)(OH₂)] ²⁺ (2, 6,6′-Me₂bpy = 6,6′-dimethyl-2,2′-bipyridine) used as key catalysts in regioselective reduction of NAD⁺ analogues were determined definitely by X-ray analysis. The yellow crystals of 1(PF₆) ₂ and orange crystals of 2(CF₃SO₃)₂ used in the X-ray analysis were obtained from aqueous solutions of 1(PF ₆)₂ and 2(CP₃SO₃)₂. The Rh-O_aqua length of 2.194(4) Å obtained for 1(PF ₆)₂ is significantly different from that of 2.157(3) Å obtained for the previously reported disorder model [Cp*Rh ^III(bpy)(0.7H₂O/0.3CH₃H)](CF₃SO ₃)₂̇0.7H₂O in which the coordinated water is replaced by a coordinated methanol. The five-membered ring involving the Rh atom and the 6,6′-Me₂bpy chelating unit in 2(CF ₃SO₃)₂ is not flat, whereas the five-membered chelate ring in 1(PF₆)₂ is nearly flat. Such a non-planar structure in 2(CF₃SO₃)₂ is ascribed to the steric repulsion between the 6,6′-Me₂bpy ligand and the Cp* ligand.

Original language	English
Pages (from-to)	639-643
Number of pages	5
Journal	Applied Organometallic Chemistry
Volume	19
Issue number	5
DOIs	https://doi.org/10.1002/aoc.837
State	Published - May 2005

Keywords

Aqua complexes
Crystal structures
Rhodium
Substituted bipyridine ligand

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10.1002/aoc.837

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@article{50a683da2c544d249ece99b69c316a65,

title = "Crystal structures of organometallic aqua complexes [Cp*Rh III(bpy)(OH2)]2+ and [Cp*Rh III(6,6′-Me2bpy)(OH2)]2+ used as key catalysts in regioselective reduction of NAD+ analogues",

abstract = "Crystal structures of organometallic aqua complexes [Cp*Rh III(bpy)(OH2)]2+ (1, Cp* = η 5-C5Me5, bpy = 2,2′-bipyridine) and [Cp*RhIII(6,6′-Me2bpy)(OH2)] 2+ (2, 6,6′-Me2bpy = 6,6′-dimethyl-2,2′-bipyridine) used as key catalysts in regioselective reduction of NAD+ analogues were determined definitely by X-ray analysis. The yellow crystals of 1(PF6) 2 and orange crystals of 2(CF3SO3)2 used in the X-ray analysis were obtained from aqueous solutions of 1(PF 6)2 and 2(CP3SO3)2. The Rh-Oaqua length of 2.194(4) {\AA} obtained for 1(PF 6)2 is significantly different from that of 2.157(3) {\AA} obtained for the previously reported disorder model [Cp*Rh III(bpy)(0.7H2O/0.3CH3H)](CF3SO 3){\.2}0.7H2O in which the coordinated water is replaced by a coordinated methanol. The five-membered ring involving the Rh atom and the 6,6′-Me2bpy chelating unit in 2(CF 3SO3)2 is not flat, whereas the five-membered chelate ring in 1(PF6)2 is nearly flat. Such a non-planar structure in 2(CF3SO3)2 is ascribed to the steric repulsion between the 6,6′-Me2bpy ligand and the Cp* ligand.",

keywords = "Aqua complexes, Crystal structures, Rhodium, Substituted bipyridine ligand",

author = "Seiji Ogo and Hideki Hayashi and Keiji Uehara and Shunichi Fukuzumi",

year = "2005",

month = may,

doi = "10.1002/aoc.837",

language = "English",

volume = "19",

pages = "639--643",

journal = "Applied Organometallic Chemistry",

issn = "0268-2605",

publisher = "John Wiley and Sons Ltd",

number = "5",

}

Crystal structures of organometallic aqua complexes [Cp*Rh ^III(bpy)(OH₂)]²⁺ and [Cp*Rh ^III(6,6′-Me₂bpy)(OH₂)]²⁺ used as key catalysts in regioselective reduction of NAD⁺ analogues. / Ogo, Seiji; Hayashi, Hideki; Uehara, Keiji et al.
In: Applied Organometallic Chemistry, Vol. 19, No. 5, 05.2005, p. 639-643.

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

TY - JOUR

T1 - Crystal structures of organometallic aqua complexes [Cp*Rh III(bpy)(OH2)]2+ and [Cp*Rh III(6,6′-Me2bpy)(OH2)]2+ used as key catalysts in regioselective reduction of NAD+ analogues

AU - Ogo, Seiji

AU - Hayashi, Hideki

AU - Uehara, Keiji

AU - Fukuzumi, Shunichi

PY - 2005/5

Y1 - 2005/5

N2 - Crystal structures of organometallic aqua complexes [Cp*Rh III(bpy)(OH2)]2+ (1, Cp* = η 5-C5Me5, bpy = 2,2′-bipyridine) and [Cp*RhIII(6,6′-Me2bpy)(OH2)] 2+ (2, 6,6′-Me2bpy = 6,6′-dimethyl-2,2′-bipyridine) used as key catalysts in regioselective reduction of NAD+ analogues were determined definitely by X-ray analysis. The yellow crystals of 1(PF6) 2 and orange crystals of 2(CF3SO3)2 used in the X-ray analysis were obtained from aqueous solutions of 1(PF 6)2 and 2(CP3SO3)2. The Rh-Oaqua length of 2.194(4) Å obtained for 1(PF 6)2 is significantly different from that of 2.157(3) Å obtained for the previously reported disorder model [Cp*Rh III(bpy)(0.7H2O/0.3CH3H)](CF3SO 3)2̇0.7H2O in which the coordinated water is replaced by a coordinated methanol. The five-membered ring involving the Rh atom and the 6,6′-Me2bpy chelating unit in 2(CF 3SO3)2 is not flat, whereas the five-membered chelate ring in 1(PF6)2 is nearly flat. Such a non-planar structure in 2(CF3SO3)2 is ascribed to the steric repulsion between the 6,6′-Me2bpy ligand and the Cp* ligand.

AB - Crystal structures of organometallic aqua complexes [Cp*Rh III(bpy)(OH2)]2+ (1, Cp* = η 5-C5Me5, bpy = 2,2′-bipyridine) and [Cp*RhIII(6,6′-Me2bpy)(OH2)] 2+ (2, 6,6′-Me2bpy = 6,6′-dimethyl-2,2′-bipyridine) used as key catalysts in regioselective reduction of NAD+ analogues were determined definitely by X-ray analysis. The yellow crystals of 1(PF6) 2 and orange crystals of 2(CF3SO3)2 used in the X-ray analysis were obtained from aqueous solutions of 1(PF 6)2 and 2(CP3SO3)2. The Rh-Oaqua length of 2.194(4) Å obtained for 1(PF 6)2 is significantly different from that of 2.157(3) Å obtained for the previously reported disorder model [Cp*Rh III(bpy)(0.7H2O/0.3CH3H)](CF3SO 3)2̇0.7H2O in which the coordinated water is replaced by a coordinated methanol. The five-membered ring involving the Rh atom and the 6,6′-Me2bpy chelating unit in 2(CF 3SO3)2 is not flat, whereas the five-membered chelate ring in 1(PF6)2 is nearly flat. Such a non-planar structure in 2(CF3SO3)2 is ascribed to the steric repulsion between the 6,6′-Me2bpy ligand and the Cp* ligand.

KW - Aqua complexes

KW - Crystal structures

KW - Rhodium

KW - Substituted bipyridine ligand

UR - http://www.scopus.com/inward/record.url?scp=17444372730&partnerID=8YFLogxK

U2 - 10.1002/aoc.837

DO - 10.1002/aoc.837

M3 - Article

AN - SCOPUS:17444372730

SN - 0268-2605

VL - 19

SP - 639

EP - 643

JO - Applied Organometallic Chemistry

JF - Applied Organometallic Chemistry

IS - 5

ER -