Formation and X-ray Structures of PCP Ligand Based Platinum(II) and Palladium(II) Macrocycles

Milko van der Boom, Michael Gozin, Yehoshoa Ben-David, Linda J W Shimon, Felix Frolow, Heinz Bernard Kraatz, David Milstein

Research output: Contribution to journalArticle

38 Citations (Scopus)

Abstract

The coordination behavior prior to C-M bond formation of the chelating aromatic PCP substrate DPPMH (3; DPPMH = l,3-bis((diphenylphosphino)methylene)mesitylene) has been studied in order to determine the factors which control the complex formation of such ligands. Reacting 3 with (RCN)2MCl2 (R = Me, Ph; M = Pd, Pt) and (COD)PtX2 (X = Cl, Me; COD = 1,5-cyclooctadiene) resulted in the formation of several 8- and 16-membered mono- and binuclear palladium(II) and platinum(II) macrocycles: trans-[(DPPMH)PdCl2]2 (5), trans-[(DPPMH)-PtCl2]2 (6), cis-(DPPMH)PtCl2 (7), cis-(DPPMH)PtMe2 (8), and cis-[(DPPMH)PtMe2]2 (9). Compounds 5-9 were fully characterized using NMR, FAB-MS, FD-MS, elemental analysis, and X-ray crystallography. Thermolysis of the bimetallic trans-[(DPPMH)PtCl2]2 (6) results in the formation of the monomeric cis-(DPPMH)PtCl2 (7). The product formation depends on the neutral- (nitriles or COD) and anionic ligands (Cl and CH3) of the metal precursor. The molecular structures of trans-[(DPPMH)PdCl2]2 (5) and cis-[(DPPMH)PtMe2]2 (9) have been determined by complete single-crystal diffraction studies. Crystal data for 5: monoclinic, space group P21 /n with a = 14.547(3) Å, b = 17.431(4) Å, c = 27.839 (5) Å, β= 99.56(2)°, V = 6961(3) Å3, and Z = 4. The structure converged to R = 0.048 and Rw = 0.049. Crystal data for 9: monoclinic, space group P21/n with a = 19.187(4) Å, b = 19.189(4) Å c = 20.705(2) Å, β= 103.41(3)°, V = 7415(3) Å3, and Z = 4. The structure refinement converged to R = 0.0977 and Rw = 0.2212.

Original languageEnglish
Pages (from-to)7068-7073
Number of pages6
JournalInorganic Chemistry
Volume35
Issue number24
Publication statusPublished - 1996

Fingerprint

Palladium
Platinum
palladium
platinum
crack opening displacement
Ligands
X rays
Nitriles
Crystals
Thermolysis
ligands
X ray crystallography
Chelation
Molecular structure
x rays
Diffraction
Metals
Nuclear magnetic resonance
Single crystals
mesitylene

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

van der Boom, M., Gozin, M., Ben-David, Y., Shimon, L. J. W., Frolow, F., Kraatz, H. B., & Milstein, D. (1996). Formation and X-ray Structures of PCP Ligand Based Platinum(II) and Palladium(II) Macrocycles. Inorganic Chemistry, 35(24), 7068-7073.

Formation and X-ray Structures of PCP Ligand Based Platinum(II) and Palladium(II) Macrocycles. / van der Boom, Milko; Gozin, Michael; Ben-David, Yehoshoa; Shimon, Linda J W; Frolow, Felix; Kraatz, Heinz Bernard; Milstein, David.

In: Inorganic Chemistry, Vol. 35, No. 24, 1996, p. 7068-7073.

Research output: Contribution to journalArticle

van der Boom, M, Gozin, M, Ben-David, Y, Shimon, LJW, Frolow, F, Kraatz, HB & Milstein, D 1996, 'Formation and X-ray Structures of PCP Ligand Based Platinum(II) and Palladium(II) Macrocycles', Inorganic Chemistry, vol. 35, no. 24, pp. 7068-7073.
van der Boom M, Gozin M, Ben-David Y, Shimon LJW, Frolow F, Kraatz HB et al. Formation and X-ray Structures of PCP Ligand Based Platinum(II) and Palladium(II) Macrocycles. Inorganic Chemistry. 1996;35(24):7068-7073.
van der Boom, Milko ; Gozin, Michael ; Ben-David, Yehoshoa ; Shimon, Linda J W ; Frolow, Felix ; Kraatz, Heinz Bernard ; Milstein, David. / Formation and X-ray Structures of PCP Ligand Based Platinum(II) and Palladium(II) Macrocycles. In: Inorganic Chemistry. 1996 ; Vol. 35, No. 24. pp. 7068-7073.
@article{5cddd8d6879e4cc590e517ed943996d6,
title = "Formation and X-ray Structures of PCP Ligand Based Platinum(II) and Palladium(II) Macrocycles",
abstract = "The coordination behavior prior to C-M bond formation of the chelating aromatic PCP substrate DPPMH (3; DPPMH = l,3-bis((diphenylphosphino)methylene)mesitylene) has been studied in order to determine the factors which control the complex formation of such ligands. Reacting 3 with (RCN)2MCl2 (R = Me, Ph; M = Pd, Pt) and (COD)PtX2 (X = Cl, Me; COD = 1,5-cyclooctadiene) resulted in the formation of several 8- and 16-membered mono- and binuclear palladium(II) and platinum(II) macrocycles: trans-[(DPPMH)PdCl2]2 (5), trans-[(DPPMH)-PtCl2]2 (6), cis-(DPPMH)PtCl2 (7), cis-(DPPMH)PtMe2 (8), and cis-[(DPPMH)PtMe2]2 (9). Compounds 5-9 were fully characterized using NMR, FAB-MS, FD-MS, elemental analysis, and X-ray crystallography. Thermolysis of the bimetallic trans-[(DPPMH)PtCl2]2 (6) results in the formation of the monomeric cis-(DPPMH)PtCl2 (7). The product formation depends on the neutral- (nitriles or COD) and anionic ligands (Cl and CH3) of the metal precursor. The molecular structures of trans-[(DPPMH)PdCl2]2 (5) and cis-[(DPPMH)PtMe2]2 (9) have been determined by complete single-crystal diffraction studies. Crystal data for 5: monoclinic, space group P21 /n with a = 14.547(3) {\AA}, b = 17.431(4) {\AA}, c = 27.839 (5) {\AA}, β= 99.56(2)°, V = 6961(3) {\AA}3, and Z = 4. The structure converged to R = 0.048 and Rw = 0.049. Crystal data for 9: monoclinic, space group P21/n with a = 19.187(4) {\AA}, b = 19.189(4) {\AA} c = 20.705(2) {\AA}, β= 103.41(3)°, V = 7415(3) {\AA}3, and Z = 4. The structure refinement converged to R = 0.0977 and Rw = 0.2212.",
author = "{van der Boom}, Milko and Michael Gozin and Yehoshoa Ben-David and Shimon, {Linda J W} and Felix Frolow and Kraatz, {Heinz Bernard} and David Milstein",
year = "1996",
language = "English",
volume = "35",
pages = "7068--7073",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "24",

}

TY - JOUR

T1 - Formation and X-ray Structures of PCP Ligand Based Platinum(II) and Palladium(II) Macrocycles

AU - van der Boom, Milko

AU - Gozin, Michael

AU - Ben-David, Yehoshoa

AU - Shimon, Linda J W

AU - Frolow, Felix

AU - Kraatz, Heinz Bernard

AU - Milstein, David

PY - 1996

Y1 - 1996

N2 - The coordination behavior prior to C-M bond formation of the chelating aromatic PCP substrate DPPMH (3; DPPMH = l,3-bis((diphenylphosphino)methylene)mesitylene) has been studied in order to determine the factors which control the complex formation of such ligands. Reacting 3 with (RCN)2MCl2 (R = Me, Ph; M = Pd, Pt) and (COD)PtX2 (X = Cl, Me; COD = 1,5-cyclooctadiene) resulted in the formation of several 8- and 16-membered mono- and binuclear palladium(II) and platinum(II) macrocycles: trans-[(DPPMH)PdCl2]2 (5), trans-[(DPPMH)-PtCl2]2 (6), cis-(DPPMH)PtCl2 (7), cis-(DPPMH)PtMe2 (8), and cis-[(DPPMH)PtMe2]2 (9). Compounds 5-9 were fully characterized using NMR, FAB-MS, FD-MS, elemental analysis, and X-ray crystallography. Thermolysis of the bimetallic trans-[(DPPMH)PtCl2]2 (6) results in the formation of the monomeric cis-(DPPMH)PtCl2 (7). The product formation depends on the neutral- (nitriles or COD) and anionic ligands (Cl and CH3) of the metal precursor. The molecular structures of trans-[(DPPMH)PdCl2]2 (5) and cis-[(DPPMH)PtMe2]2 (9) have been determined by complete single-crystal diffraction studies. Crystal data for 5: monoclinic, space group P21 /n with a = 14.547(3) Å, b = 17.431(4) Å, c = 27.839 (5) Å, β= 99.56(2)°, V = 6961(3) Å3, and Z = 4. The structure converged to R = 0.048 and Rw = 0.049. Crystal data for 9: monoclinic, space group P21/n with a = 19.187(4) Å, b = 19.189(4) Å c = 20.705(2) Å, β= 103.41(3)°, V = 7415(3) Å3, and Z = 4. The structure refinement converged to R = 0.0977 and Rw = 0.2212.

AB - The coordination behavior prior to C-M bond formation of the chelating aromatic PCP substrate DPPMH (3; DPPMH = l,3-bis((diphenylphosphino)methylene)mesitylene) has been studied in order to determine the factors which control the complex formation of such ligands. Reacting 3 with (RCN)2MCl2 (R = Me, Ph; M = Pd, Pt) and (COD)PtX2 (X = Cl, Me; COD = 1,5-cyclooctadiene) resulted in the formation of several 8- and 16-membered mono- and binuclear palladium(II) and platinum(II) macrocycles: trans-[(DPPMH)PdCl2]2 (5), trans-[(DPPMH)-PtCl2]2 (6), cis-(DPPMH)PtCl2 (7), cis-(DPPMH)PtMe2 (8), and cis-[(DPPMH)PtMe2]2 (9). Compounds 5-9 were fully characterized using NMR, FAB-MS, FD-MS, elemental analysis, and X-ray crystallography. Thermolysis of the bimetallic trans-[(DPPMH)PtCl2]2 (6) results in the formation of the monomeric cis-(DPPMH)PtCl2 (7). The product formation depends on the neutral- (nitriles or COD) and anionic ligands (Cl and CH3) of the metal precursor. The molecular structures of trans-[(DPPMH)PdCl2]2 (5) and cis-[(DPPMH)PtMe2]2 (9) have been determined by complete single-crystal diffraction studies. Crystal data for 5: monoclinic, space group P21 /n with a = 14.547(3) Å, b = 17.431(4) Å, c = 27.839 (5) Å, β= 99.56(2)°, V = 6961(3) Å3, and Z = 4. The structure converged to R = 0.048 and Rw = 0.049. Crystal data for 9: monoclinic, space group P21/n with a = 19.187(4) Å, b = 19.189(4) Å c = 20.705(2) Å, β= 103.41(3)°, V = 7415(3) Å3, and Z = 4. The structure refinement converged to R = 0.0977 and Rw = 0.2212.

UR - http://www.scopus.com/inward/record.url?scp=0000274161&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0000274161&partnerID=8YFLogxK

M3 - Article

AN - SCOPUS:0000274161

VL - 35

SP - 7068

EP - 7073

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 24

ER -