Water-Soluble Organometallic Compounds. 6. 1 Synthesis, Spectral Properties, and Crystal Structures of Complexes of 1,3,5-Triaza-7-phosphaadamantane with Group 10 Metals

Donald J. Darensbourg, Tara J. Decuir, Nicole White Stafford, Jeffrey B. Robertson, Jennifer D. Draper, Joseph H. Reibenspies, A. Kathó, Ferenc Joó

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Abstract

The syntheses of a variety of group 10 metal complexes of the water-soluble phosphine triazaphosphaadamantane (PTA) are described. Treatment of Ni(NO 3) 2 with NaNO 2 and PTA provides the nitrosyl complex [Ni(NO)-(PTA) 3]NO 3 (1). Complex 1 is soluble in water, DMSO, and CH 3CN but insoluble in THF, acetone, or hydrocarbons. X-ray crystallography shows the nitrosyl ligand to be coordinated in a near linear mode (ZNi-N-O = 171.5(4)̊) with a Ni-N bond length of 1.653(4) Å. Concordantly, the v(NO) vibration in H 2O occurs at 1830 cm -1. The series of zerovalent M(PTA) 4 (M = Ni, Pd, Pt) complexes, 2, 3, and 6 have been prepared in good yields by several procedures: (i) the ligand exchange reaction of Ni(cod) 2 with PTA; (ii) the reduction of PdCl 2 or PtCl 2 with hydrazine in the presence of PTA; and (iii) the ligand exchange reaction of Pt(PPh 3) 4 with PTA. All three derivatives are very water soluble (0.30 M) and resistant to PTA dissociation in solution at ambient temperature. Complexes 2, 3, and 6 can be crystallized from 0.10 M HCl to afford the nitrogen-protonated derivatives, [M(PTAH) 4]Cl 4. These salts were characterized by X-ray crystallography and shown to exist as slightly distorted tetrahedra with one nitrogen atom of each PTA ligand protonated. The M-P bond lengths are shorter than those found in related derivatives containing poorer electron-donating and/or sterically more encumbering phosphine ligands. The cis-MCl 2(PTA) 2 (M = Pd and Pt) derivatives, 4 and 7, were obtained by the metathesis reaction of (NH 4) 2PdCl 4 or K 2PtCl 4 with PTA in refluxing ethanol. When the palladium reaction was carried out in a large excess of PTA, formation of the zerovalent Pd(PTA) 4 complex occurred via the intermediacy of the [Pd(PTA) 3Cl] + cation as indicated by 31P NMR and mass spectrometry. The X-ray structures of the Pd(II) and Pt(II) derivatives, cis-PdCl 2(PTA) 2 and [cis-PtCl 2(PTAH) 2]Cl 2, revealed these to exist as slightly distorted square planar complexes where the P-M-P angles are expanded to 94.4°. The platinum derivative, which contains the nitrogen protonated PTA ligands, displays an extensive array of hydrogen bonding and electrostatic interactions involving water, PTA, and HCl.

Original languageEnglish
Pages (from-to)4218-4226
Number of pages9
JournalInorganic Chemistry
Volume36
Issue number19
Publication statusPublished - 1997

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phosphine
Organometallic Compounds
organometallic compounds
phosphines
Crystal structure
Metals
crystal structure
Water
synthesis
metals
water
Ligands
Derivatives
ligands
1,3,5-triaza-7-phosphaadamantane
Nitrogen
hydrazine
X ray crystallography

ASJC Scopus subject areas

  • Inorganic Chemistry

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Darensbourg, D. J., Decuir, T. J., Stafford, N. W., Robertson, J. B., Draper, J. D., Reibenspies, J. H., ... Joó, F. (1997). Water-Soluble Organometallic Compounds. 6. 1 Synthesis, Spectral Properties, and Crystal Structures of Complexes of 1,3,5-Triaza-7-phosphaadamantane with Group 10 Metals. Inorganic Chemistry, 36(19), 4218-4226.

Water-Soluble Organometallic Compounds. 6. 1 Synthesis, Spectral Properties, and Crystal Structures of Complexes of 1,3,5-Triaza-7-phosphaadamantane with Group 10 Metals. / Darensbourg, Donald J.; Decuir, Tara J.; Stafford, Nicole White; Robertson, Jeffrey B.; Draper, Jennifer D.; Reibenspies, Joseph H.; Kathó, A.; Joó, Ferenc.

In: Inorganic Chemistry, Vol. 36, No. 19, 1997, p. 4218-4226.

Research output: Contribution to journalArticle

Darensbourg, DJ, Decuir, TJ, Stafford, NW, Robertson, JB, Draper, JD, Reibenspies, JH, Kathó, A & Joó, F 1997, 'Water-Soluble Organometallic Compounds. 6. 1 Synthesis, Spectral Properties, and Crystal Structures of Complexes of 1,3,5-Triaza-7-phosphaadamantane with Group 10 Metals', Inorganic Chemistry, vol. 36, no. 19, pp. 4218-4226.
Darensbourg, Donald J. ; Decuir, Tara J. ; Stafford, Nicole White ; Robertson, Jeffrey B. ; Draper, Jennifer D. ; Reibenspies, Joseph H. ; Kathó, A. ; Joó, Ferenc. / Water-Soluble Organometallic Compounds. 6. 1 Synthesis, Spectral Properties, and Crystal Structures of Complexes of 1,3,5-Triaza-7-phosphaadamantane with Group 10 Metals. In: Inorganic Chemistry. 1997 ; Vol. 36, No. 19. pp. 4218-4226.
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abstract = "The syntheses of a variety of group 10 metal complexes of the water-soluble phosphine triazaphosphaadamantane (PTA) are described. Treatment of Ni(NO 3) 2 with NaNO 2 and PTA provides the nitrosyl complex [Ni(NO)-(PTA) 3]NO 3 (1). Complex 1 is soluble in water, DMSO, and CH 3CN but insoluble in THF, acetone, or hydrocarbons. X-ray crystallography shows the nitrosyl ligand to be coordinated in a near linear mode (ZNi-N-O = 171.5(4)̊) with a Ni-N bond length of 1.653(4) {\AA}. Concordantly, the v(NO) vibration in H 2O occurs at 1830 cm -1. The series of zerovalent M(PTA) 4 (M = Ni, Pd, Pt) complexes, 2, 3, and 6 have been prepared in good yields by several procedures: (i) the ligand exchange reaction of Ni(cod) 2 with PTA; (ii) the reduction of PdCl 2 or PtCl 2 with hydrazine in the presence of PTA; and (iii) the ligand exchange reaction of Pt(PPh 3) 4 with PTA. All three derivatives are very water soluble (0.30 M) and resistant to PTA dissociation in solution at ambient temperature. Complexes 2, 3, and 6 can be crystallized from 0.10 M HCl to afford the nitrogen-protonated derivatives, [M(PTAH) 4]Cl 4. These salts were characterized by X-ray crystallography and shown to exist as slightly distorted tetrahedra with one nitrogen atom of each PTA ligand protonated. The M-P bond lengths are shorter than those found in related derivatives containing poorer electron-donating and/or sterically more encumbering phosphine ligands. The cis-MCl 2(PTA) 2 (M = Pd and Pt) derivatives, 4 and 7, were obtained by the metathesis reaction of (NH 4) 2PdCl 4 or K 2PtCl 4 with PTA in refluxing ethanol. When the palladium reaction was carried out in a large excess of PTA, formation of the zerovalent Pd(PTA) 4 complex occurred via the intermediacy of the [Pd(PTA) 3Cl] + cation as indicated by 31P NMR and mass spectrometry. The X-ray structures of the Pd(II) and Pt(II) derivatives, cis-PdCl 2(PTA) 2 and [cis-PtCl 2(PTAH) 2]Cl 2, revealed these to exist as slightly distorted square planar complexes where the P-M-P angles are expanded to 94.4°. The platinum derivative, which contains the nitrogen protonated PTA ligands, displays an extensive array of hydrogen bonding and electrostatic interactions involving water, PTA, and HCl.",
author = "Darensbourg, {Donald J.} and Decuir, {Tara J.} and Stafford, {Nicole White} and Robertson, {Jeffrey B.} and Draper, {Jennifer D.} and Reibenspies, {Joseph H.} and A. Kath{\'o} and Ferenc Jo{\'o}",
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T1 - Water-Soluble Organometallic Compounds. 6. 1 Synthesis, Spectral Properties, and Crystal Structures of Complexes of 1,3,5-Triaza-7-phosphaadamantane with Group 10 Metals

AU - Darensbourg, Donald J.

AU - Decuir, Tara J.

AU - Stafford, Nicole White

AU - Robertson, Jeffrey B.

AU - Draper, Jennifer D.

AU - Reibenspies, Joseph H.

AU - Kathó, A.

AU - Joó, Ferenc

PY - 1997

Y1 - 1997

N2 - The syntheses of a variety of group 10 metal complexes of the water-soluble phosphine triazaphosphaadamantane (PTA) are described. Treatment of Ni(NO 3) 2 with NaNO 2 and PTA provides the nitrosyl complex [Ni(NO)-(PTA) 3]NO 3 (1). Complex 1 is soluble in water, DMSO, and CH 3CN but insoluble in THF, acetone, or hydrocarbons. X-ray crystallography shows the nitrosyl ligand to be coordinated in a near linear mode (ZNi-N-O = 171.5(4)̊) with a Ni-N bond length of 1.653(4) Å. Concordantly, the v(NO) vibration in H 2O occurs at 1830 cm -1. The series of zerovalent M(PTA) 4 (M = Ni, Pd, Pt) complexes, 2, 3, and 6 have been prepared in good yields by several procedures: (i) the ligand exchange reaction of Ni(cod) 2 with PTA; (ii) the reduction of PdCl 2 or PtCl 2 with hydrazine in the presence of PTA; and (iii) the ligand exchange reaction of Pt(PPh 3) 4 with PTA. All three derivatives are very water soluble (0.30 M) and resistant to PTA dissociation in solution at ambient temperature. Complexes 2, 3, and 6 can be crystallized from 0.10 M HCl to afford the nitrogen-protonated derivatives, [M(PTAH) 4]Cl 4. These salts were characterized by X-ray crystallography and shown to exist as slightly distorted tetrahedra with one nitrogen atom of each PTA ligand protonated. The M-P bond lengths are shorter than those found in related derivatives containing poorer electron-donating and/or sterically more encumbering phosphine ligands. The cis-MCl 2(PTA) 2 (M = Pd and Pt) derivatives, 4 and 7, were obtained by the metathesis reaction of (NH 4) 2PdCl 4 or K 2PtCl 4 with PTA in refluxing ethanol. When the palladium reaction was carried out in a large excess of PTA, formation of the zerovalent Pd(PTA) 4 complex occurred via the intermediacy of the [Pd(PTA) 3Cl] + cation as indicated by 31P NMR and mass spectrometry. The X-ray structures of the Pd(II) and Pt(II) derivatives, cis-PdCl 2(PTA) 2 and [cis-PtCl 2(PTAH) 2]Cl 2, revealed these to exist as slightly distorted square planar complexes where the P-M-P angles are expanded to 94.4°. The platinum derivative, which contains the nitrogen protonated PTA ligands, displays an extensive array of hydrogen bonding and electrostatic interactions involving water, PTA, and HCl.

AB - The syntheses of a variety of group 10 metal complexes of the water-soluble phosphine triazaphosphaadamantane (PTA) are described. Treatment of Ni(NO 3) 2 with NaNO 2 and PTA provides the nitrosyl complex [Ni(NO)-(PTA) 3]NO 3 (1). Complex 1 is soluble in water, DMSO, and CH 3CN but insoluble in THF, acetone, or hydrocarbons. X-ray crystallography shows the nitrosyl ligand to be coordinated in a near linear mode (ZNi-N-O = 171.5(4)̊) with a Ni-N bond length of 1.653(4) Å. Concordantly, the v(NO) vibration in H 2O occurs at 1830 cm -1. The series of zerovalent M(PTA) 4 (M = Ni, Pd, Pt) complexes, 2, 3, and 6 have been prepared in good yields by several procedures: (i) the ligand exchange reaction of Ni(cod) 2 with PTA; (ii) the reduction of PdCl 2 or PtCl 2 with hydrazine in the presence of PTA; and (iii) the ligand exchange reaction of Pt(PPh 3) 4 with PTA. All three derivatives are very water soluble (0.30 M) and resistant to PTA dissociation in solution at ambient temperature. Complexes 2, 3, and 6 can be crystallized from 0.10 M HCl to afford the nitrogen-protonated derivatives, [M(PTAH) 4]Cl 4. These salts were characterized by X-ray crystallography and shown to exist as slightly distorted tetrahedra with one nitrogen atom of each PTA ligand protonated. The M-P bond lengths are shorter than those found in related derivatives containing poorer electron-donating and/or sterically more encumbering phosphine ligands. The cis-MCl 2(PTA) 2 (M = Pd and Pt) derivatives, 4 and 7, were obtained by the metathesis reaction of (NH 4) 2PdCl 4 or K 2PtCl 4 with PTA in refluxing ethanol. When the palladium reaction was carried out in a large excess of PTA, formation of the zerovalent Pd(PTA) 4 complex occurred via the intermediacy of the [Pd(PTA) 3Cl] + cation as indicated by 31P NMR and mass spectrometry. The X-ray structures of the Pd(II) and Pt(II) derivatives, cis-PdCl 2(PTA) 2 and [cis-PtCl 2(PTAH) 2]Cl 2, revealed these to exist as slightly distorted square planar complexes where the P-M-P angles are expanded to 94.4°. The platinum derivative, which contains the nitrogen protonated PTA ligands, displays an extensive array of hydrogen bonding and electrostatic interactions involving water, PTA, and HCl.

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