Further studies of metal-metal bonded oligomers of rhodium(I) isocyanide complexes. Crystal structure analysis of [Rh2(CNPh)8](BPh4)2

Kent R. Mann, Nathan S Lewis, Roger M. Williams, Harry B. Gray, J. G. Gordon

Research output: Contribution to journalArticle

134 Citations (Scopus)

Abstract

The room-temperature electronic absorption spectra of [Rh(CNR)4]+ (R = Ph, i-Pr, cyclohexyl, t-Bu, vinyl) in solution do not follow Beer's law. This behavior has been attributed to oligomerization of Rh(CNR)4+ units to form species of the type [Rhn(CNR)4n]n+. Band maxima attributable to oligomers are as follows: R = Ph, 568 nm (n = 2), 727 nm (n = 3), in acetonitrile solution; R = t-Bu, 490 nm (n = 2), 622 nm (n = 3), in aqueous solution; R = i-Pr, 495 nm (n = 2), 610 nm (n = 3), in aqueous solution; R = cyclohexyl, 516 nm (n = 2), in acetonitrile solution; R = vinyl, 555 nm (n = 2), 715 nm (n = 3), 962 nm (n = 4), in aqueous solution. The molar extinction coefficients (εn) and formation constants Kn-1 have been obtained for R = Ph in acetonitrile solution and R = t-Bu in aqueous solution. Parameter values are as follows: for R = Ph, K1 = 35 (15) M-1, ε2 = 1.05 (20) × 104, ε3K2 = 1.83 (40) × 105 M-1; for R = t-Bu, K1 = 250 (125) M-1, ε2 = 1.69 (34) × 104. The x-ray crystal structure of Rh(CNPh)4BPh4 has been completed (final R = 0.057). The compound crystallizes in the Pbcn space group (a = 23.80 (1), b = 19.23 (1), c = 19.08 (1) Å) with four discrete cationic [Rh2(CNPh)8]2+ units and eight BPh4- anions. The dimeric cation has idealized D4d symmetry; the two [Rh(CNPh)4]+ units are bonded face to face so as to give a staggered configuration of ligands. The Rh-Rh distance is 3.193 Å. The electronic absorption spectra of D4d [Rh2(CNR)8]2+ and assumed D4h [Rh3(CNR)12]3+ complexes are interpreted in terms of the interactions expected between the occupied a1g(dz2) and unoccupied a2u[pz, π*(CNR)] monomer orbitals. The lowest band in each of the [Rh2(CNR)8]2+ complexes is assigned to the allowed 1b2 → 2a1 transition. In the spectra of [Rh3(CNR)12]3+ complexes, the lowest band is attributed to 2a1g → 2a2u.

Original languageEnglish
Pages (from-to)828-834
Number of pages7
JournalInorganic Chemistry
Volume17
Issue number4
Publication statusPublished - 1978

Fingerprint

Rhodium
Cyanides
rhodium
oligomers
Oligomers
Crystal structure
Metals
aqueous solutions
acetonitrile
crystal structure
electronic spectra
metals
absorption spectra
Beer law
Absorption spectra
extinction
monomers
anions
cations
orbitals

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Further studies of metal-metal bonded oligomers of rhodium(I) isocyanide complexes. Crystal structure analysis of [Rh2(CNPh)8](BPh4)2. / Mann, Kent R.; Lewis, Nathan S; Williams, Roger M.; Gray, Harry B.; Gordon, J. G.

In: Inorganic Chemistry, Vol. 17, No. 4, 1978, p. 828-834.

Research output: Contribution to journalArticle

@article{c58dada3226443bbbcece5bcd61906a2,
title = "Further studies of metal-metal bonded oligomers of rhodium(I) isocyanide complexes. Crystal structure analysis of [Rh2(CNPh)8](BPh4)2",
abstract = "The room-temperature electronic absorption spectra of [Rh(CNR)4]+ (R = Ph, i-Pr, cyclohexyl, t-Bu, vinyl) in solution do not follow Beer's law. This behavior has been attributed to oligomerization of Rh(CNR)4+ units to form species of the type [Rhn(CNR)4n]n+. Band maxima attributable to oligomers are as follows: R = Ph, 568 nm (n = 2), 727 nm (n = 3), in acetonitrile solution; R = t-Bu, 490 nm (n = 2), 622 nm (n = 3), in aqueous solution; R = i-Pr, 495 nm (n = 2), 610 nm (n = 3), in aqueous solution; R = cyclohexyl, 516 nm (n = 2), in acetonitrile solution; R = vinyl, 555 nm (n = 2), 715 nm (n = 3), 962 nm (n = 4), in aqueous solution. The molar extinction coefficients (εn) and formation constants Kn-1 have been obtained for R = Ph in acetonitrile solution and R = t-Bu in aqueous solution. Parameter values are as follows: for R = Ph, K1 = 35 (15) M-1, ε2 = 1.05 (20) × 104, ε3K2 = 1.83 (40) × 105 M-1; for R = t-Bu, K1 = 250 (125) M-1, ε2 = 1.69 (34) × 104. The x-ray crystal structure of Rh(CNPh)4BPh4 has been completed (final R = 0.057). The compound crystallizes in the Pbcn space group (a = 23.80 (1), b = 19.23 (1), c = 19.08 (1) {\AA}) with four discrete cationic [Rh2(CNPh)8]2+ units and eight BPh4- anions. The dimeric cation has idealized D4d symmetry; the two [Rh(CNPh)4]+ units are bonded face to face so as to give a staggered configuration of ligands. The Rh-Rh distance is 3.193 {\AA}. The electronic absorption spectra of D4d [Rh2(CNR)8]2+ and assumed D4h [Rh3(CNR)12]3+ complexes are interpreted in terms of the interactions expected between the occupied a1g(dz2) and unoccupied a2u[pz, π*(CNR)] monomer orbitals. The lowest band in each of the [Rh2(CNR)8]2+ complexes is assigned to the allowed 1b2 → 2a1 transition. In the spectra of [Rh3(CNR)12]3+ complexes, the lowest band is attributed to 2a1g → 2a2u.",
author = "Mann, {Kent R.} and Lewis, {Nathan S} and Williams, {Roger M.} and Gray, {Harry B.} and Gordon, {J. G.}",
year = "1978",
language = "English",
volume = "17",
pages = "828--834",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "4",

}

TY - JOUR

T1 - Further studies of metal-metal bonded oligomers of rhodium(I) isocyanide complexes. Crystal structure analysis of [Rh2(CNPh)8](BPh4)2

AU - Mann, Kent R.

AU - Lewis, Nathan S

AU - Williams, Roger M.

AU - Gray, Harry B.

AU - Gordon, J. G.

PY - 1978

Y1 - 1978

N2 - The room-temperature electronic absorption spectra of [Rh(CNR)4]+ (R = Ph, i-Pr, cyclohexyl, t-Bu, vinyl) in solution do not follow Beer's law. This behavior has been attributed to oligomerization of Rh(CNR)4+ units to form species of the type [Rhn(CNR)4n]n+. Band maxima attributable to oligomers are as follows: R = Ph, 568 nm (n = 2), 727 nm (n = 3), in acetonitrile solution; R = t-Bu, 490 nm (n = 2), 622 nm (n = 3), in aqueous solution; R = i-Pr, 495 nm (n = 2), 610 nm (n = 3), in aqueous solution; R = cyclohexyl, 516 nm (n = 2), in acetonitrile solution; R = vinyl, 555 nm (n = 2), 715 nm (n = 3), 962 nm (n = 4), in aqueous solution. The molar extinction coefficients (εn) and formation constants Kn-1 have been obtained for R = Ph in acetonitrile solution and R = t-Bu in aqueous solution. Parameter values are as follows: for R = Ph, K1 = 35 (15) M-1, ε2 = 1.05 (20) × 104, ε3K2 = 1.83 (40) × 105 M-1; for R = t-Bu, K1 = 250 (125) M-1, ε2 = 1.69 (34) × 104. The x-ray crystal structure of Rh(CNPh)4BPh4 has been completed (final R = 0.057). The compound crystallizes in the Pbcn space group (a = 23.80 (1), b = 19.23 (1), c = 19.08 (1) Å) with four discrete cationic [Rh2(CNPh)8]2+ units and eight BPh4- anions. The dimeric cation has idealized D4d symmetry; the two [Rh(CNPh)4]+ units are bonded face to face so as to give a staggered configuration of ligands. The Rh-Rh distance is 3.193 Å. The electronic absorption spectra of D4d [Rh2(CNR)8]2+ and assumed D4h [Rh3(CNR)12]3+ complexes are interpreted in terms of the interactions expected between the occupied a1g(dz2) and unoccupied a2u[pz, π*(CNR)] monomer orbitals. The lowest band in each of the [Rh2(CNR)8]2+ complexes is assigned to the allowed 1b2 → 2a1 transition. In the spectra of [Rh3(CNR)12]3+ complexes, the lowest band is attributed to 2a1g → 2a2u.

AB - The room-temperature electronic absorption spectra of [Rh(CNR)4]+ (R = Ph, i-Pr, cyclohexyl, t-Bu, vinyl) in solution do not follow Beer's law. This behavior has been attributed to oligomerization of Rh(CNR)4+ units to form species of the type [Rhn(CNR)4n]n+. Band maxima attributable to oligomers are as follows: R = Ph, 568 nm (n = 2), 727 nm (n = 3), in acetonitrile solution; R = t-Bu, 490 nm (n = 2), 622 nm (n = 3), in aqueous solution; R = i-Pr, 495 nm (n = 2), 610 nm (n = 3), in aqueous solution; R = cyclohexyl, 516 nm (n = 2), in acetonitrile solution; R = vinyl, 555 nm (n = 2), 715 nm (n = 3), 962 nm (n = 4), in aqueous solution. The molar extinction coefficients (εn) and formation constants Kn-1 have been obtained for R = Ph in acetonitrile solution and R = t-Bu in aqueous solution. Parameter values are as follows: for R = Ph, K1 = 35 (15) M-1, ε2 = 1.05 (20) × 104, ε3K2 = 1.83 (40) × 105 M-1; for R = t-Bu, K1 = 250 (125) M-1, ε2 = 1.69 (34) × 104. The x-ray crystal structure of Rh(CNPh)4BPh4 has been completed (final R = 0.057). The compound crystallizes in the Pbcn space group (a = 23.80 (1), b = 19.23 (1), c = 19.08 (1) Å) with four discrete cationic [Rh2(CNPh)8]2+ units and eight BPh4- anions. The dimeric cation has idealized D4d symmetry; the two [Rh(CNPh)4]+ units are bonded face to face so as to give a staggered configuration of ligands. The Rh-Rh distance is 3.193 Å. The electronic absorption spectra of D4d [Rh2(CNR)8]2+ and assumed D4h [Rh3(CNR)12]3+ complexes are interpreted in terms of the interactions expected between the occupied a1g(dz2) and unoccupied a2u[pz, π*(CNR)] monomer orbitals. The lowest band in each of the [Rh2(CNR)8]2+ complexes is assigned to the allowed 1b2 → 2a1 transition. In the spectra of [Rh3(CNR)12]3+ complexes, the lowest band is attributed to 2a1g → 2a2u.

UR - http://www.scopus.com/inward/record.url?scp=0000180767&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0000180767&partnerID=8YFLogxK

M3 - Article

AN - SCOPUS:0000180767

VL - 17

SP - 828

EP - 834

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 4

ER -