Sulfur Donor

14,000,000 Leading Edge Experts on the ideXlab platform

Scan Science and Technology

Contact Leading Edge Experts & Companies

Scan Science and Technology

Contact Leading Edge Experts & Companies

The Experts below are selected from a list of 291 Experts worldwide ranked by ideXlab platform

Robert R. Holmes - One of the best experts on this subject based on the ideXlab platform.

  • The First Hydrogen Bonded Anionic Phosphates Exhibiting Sulfur Donor Coordination1
    Inorganic Chemistry, 1999
    Co-Authors: A. Chandrasekaran, Paul Sood, Roberta O. Day, Robert R. Holmes
    Abstract:

    We have synthesized and structurally characterized the first anionic phosphates undergoing Sulfur Donor action in the presence of hydrogen bonding. As a consequence, these phosphates increase their coordination geometry toward a trigonal bipyramid. It is suggested that such action may occur at active sites of phosphoryl transfer enzyme containing anionic phosphate substrates.

  • Pentacoordinated Organo and Hydrido Cyclic Silanes via Sulfur Donor Action1
    Organometallics, 1999
    Co-Authors: Ramil-marcelo L. Mercado, A. Chandrasekaran, Roberta O. Day, Robert R. Holmes
    Abstract:

    The new cyclic organosilanes S(C10H6O)2SiMe2 (1) and S(C10H6O)2SiPh2 (2) were obtained by the reaction of R2Si(NMe2)2 (R = Me, Ph) with thiobis(2,2‘-naphthol), while S[Me2C6H2O]2SiH(Me) (3) and S[(t-Bu)MeC6H2O]2SiH(Me) (4) were formed by reaction of Cl2SiH(Me) with the appropriate diol in the presence of Et3N. Characterization was achieved by 29Si and 1H solution NMR, 29Si solid-state NMR, and X-ray structural studies. As a result of Sulfur Donor interaction, pentacoordinate geometries were obtained where 3 and 4 were displaced further toward a trigonal bipyramid (TBP) compared to 1 and 2. Variable-temperature NMR spectra showed 1 to be fluxional with an activation energy of 9.4 kcal/mol. An exchange mechanism involving rupture of the Si−S Donor interaction accompanying a ring pseudorotation is postulated. The less symmetric silanes 3 and 4 do not exchange, as indicated by the 1H NMR data. Comparison of the degree of Si−S Donor interaction of 1−4 with that of related cyclic organosilanes possessing Si−O a...

  • Increased coordination via Sulfur Donor action in cyclic pentaoxyphosphoranes and the parent cyclic phosphite. Influence of pentafluorophenoxy ligands
    Inorganic chemistry, 1998
    Co-Authors: Paul Sood, A. Chandrasekaran, Roberta O. Day, Robert R. Holmes
    Abstract:

    The pentafluorophenoxy ligand was introduced into the new cyclic pentaoxyphosphoranes S[(t-Bu)MeC(6)H(2)O](2)P(OC(6)F(5))(O(2)C(6)Cl(4)) (1), S[(t-Bu)MeC(6)H(2)O](2)P(OC(6)F(5))(O(2)C(14)H(8)) (2), and S[(t-Bu)MeC(6)H(2)O](2)P(OC(6)F(5))(3) (3). X-ray analysis revealed hexacoordinate structures formed by Sulfur Donor action present as a bridging atom in flexible eight-membered rings for 1-3. X-ray analysis showed that Sulfur coordination also occurred with the same type of ring system as part of the phosphite S[(t-Bu)MeC(6)H(2)O](2)P(OC(6)F(5)) (4) to give a pseudo-trigonal-bipyramidal geometry. The pentafluorophenoxy ligand present in the oxyphosphoranes 1-3 as well as in the phosphite 4 acts comparably to a chlorine atom in its ability to enhance phosphorus electrophilicity as measured by the degree of P-S coordination and geometrical displacement toward a more highly coordinated state. The phosphite 4 has a P-S Donor distance of 2.876(2) A, considerably longer than the range of P-S distances from 2.366(3) to 2.495(2) A obtained for the pentaoxyphosphoranes 1-3. These data express quantitatively the relative electrophilicity of phosphorus as a function of coordination number and substituent composition.

  • Hexacoordination via Sulfur Donor Action in Bicyclic Pentaoxyphosphoranes(1).
    Inorganic chemistry, 1997
    Co-Authors: Paul Sood, A. Chandrasekaran, T. K. Prakasha, Roberta O. Day, Robert R. Holmes
    Abstract:

    New bicyclic oxyphosphoranes, S[(t-Bu)MeC(6)H(2)O](2)P(OC(6)H(5))(O(2)C(6)H(3)F) (1) and S[(t-Bu)MeC(6)H(2)O](2)P(OC(6)H(5))(O(2)C(6)H(4)) (3), were synthesized by displacement reactions of a monocyclic pentaoxyphosphorane by a diol, and S[(t-Bu)(2)C(6)H(2)O](2)P(OCH(2)CF(3))(O(2)C(6)Cl(4)) (2) and S[(t-Bu)(2)C(6)H(2)O](2)P(C(6)H(5))(O(2)C(6)Cl(4)) (4), by oxidative addition reactions of a phosphite or phosphine with tetrachlorobenzoquinone. X-ray studies revealed hexacoordinated structures formed by the presence of a Sulfur Donor atom incorporated in a flexible eight-membered ring. The structures were displaced along a coordinate from a square pyramid toward an octahedron. (31)P and (1)H NMR data are also reported. Comparisons are made between bicyclic tetraoxyphosphoranes and monocyclic and bicyclic pentaoxyphosphoranes which show the importance of ligand electronegativity in increasing the degree of hexacoordination. Of the various series now studied, the extent of Sulfur Donor atom coordination increases in the following order: phosphates < phosphites < oxyphosphoranes. It is concluded that, in general, Sulfur Donor atom coordination will take place with phosphorus in any of the common coordination geometries in the presence of sufficiently electronegative ligands.

  • pentacoordination and pseudopentacoordination via Sulfur Donor action in cyclic phosphates and phosphites1
    Inorganic Chemistry, 1997
    Co-Authors: David J Sherlock, A. Chandrasekaran, Roberta O. Day, Robert R. Holmes
    Abstract:

    New cyclic chlorophosphites S[(t-Bu)2C6H2O]2PCl (3) and CH2[(t-Bu)MeC6H2O]2PCl (6) and the cyclic phosphate S[(t-Bu)MeC6H2O]2P(O)Cl (4) were synthesized from the reaction of PCl3 or POCl3 with the ...

Akira Nagasawa - One of the best experts on this subject based on the ideXlab platform.

  • syntheses and properties of dinuclear group 6 metal complexes with the zwitterionic Sulfur Donor ligand bis n n diethylamino carbeniumdithiocarboxylate
    Organometallics, 2013
    Co-Authors: Tomoaki Sugaya, Takeshi Ohba, Shigeru Mashima, Takashi Fujihara, Kei Unoura, Akira Nagasawa
    Abstract:

    A class of dinuclear group 6 metal complexes [{M0(CO)5}2(μ-S,S′-EtL)] (M = Cr, Mo, W) with the asymmetrically bridged zwitterionic Sulfur Donor bis(N,N-diethylamino)carbeniumdithiocarboxylate (EtL) was prepared by photoreaction of [M0(CO)6] with EtL in hexane–CH2Cl2 for Cr and Mo or THF for W. The same structure in a syn–anti coordination mode was revealed by X-ray analyses for chromium(0) and tungsten(0) complexes, 1 and 3, respectively, and speculated from various analytical data for the molybdenum(0) complex 2. The pertinent criteria for the coordination mode are found to be the wavenumber of the asymmetric stretching vibration of the −CS2 moiety in the solid state and the ligand-based reduction potential in solution. Complexes 1 and 3 showed quasi-reversible reduction waves, which are assigned to a two-step, one-electron reduction process derived from the bridging EtL. In a series of [Cr(CO)5L] complexes (L = monodentate ligand), the 13C NMR chemical shifts of the trans-to-L carbonyl group showed the ...

  • Syntheses and Properties of Dinuclear Group 6 Metal Complexes with the Zwitterionic Sulfur Donor Ligand Bis(N,N-diethylamino)carbeniumdithiocarboxylate
    Organometallics, 2013
    Co-Authors: Tomoaki Sugaya, Takeshi Ohba, Shigeru Mashima, Takashi Fujihara, Kei Unoura, Fumiya Sai, Akira Nagasawa
    Abstract:

    A class of dinuclear group 6 metal complexes [{M0(CO)5}2(μ-S,S′-EtL)] (M = Cr, Mo, W) with the asymmetrically bridged zwitterionic Sulfur Donor bis(N,N-diethylamino)carbeniumdithiocarboxylate (EtL) was prepared by photoreaction of [M0(CO)6] with EtL in hexane–CH2Cl2 for Cr and Mo or THF for W. The same structure in a syn–anti coordination mode was revealed by X-ray analyses for chromium(0) and tungsten(0) complexes, 1 and 3, respectively, and speculated from various analytical data for the molybdenum(0) complex 2. The pertinent criteria for the coordination mode are found to be the wavenumber of the asymmetric stretching vibration of the −CS2 moiety in the solid state and the ligand-based reduction potential in solution. Complexes 1 and 3 showed quasi-reversible reduction waves, which are assigned to a two-step, one-electron reduction process derived from the bridging EtL. In a series of [Cr(CO)5L] complexes (L = monodentate ligand), the 13C NMR chemical shifts of the trans-to-L carbonyl group showed the ...

  • Rhenium(I) carbonyl complexes of bis(N,N-diethylamino)carbeniumdithiocarboxylate, a novel inner-salt type Sulfur Donor ligand. Spectroscopic and structural studies
    Inorganica Chimica Acta, 2002
    Co-Authors: Sangeeta Ray Banerjee, Akira Nagasawa, Jon Zubieta
    Abstract:

    Abstract The reaction of the inner-salt SS Donor ligand, bis( N , N -diethylamino)carbeniumdithiocarboxylate, Et 4 L, with [Re(CO) 5 Cl] afforded a red colored dinuclear rhenium(I) complex [Re 2 (CO) 6 (μ-Cl) 2 (μ-(Et 4 L)] in excellent yield, along with the mononuclear complex [Re(CO) 3 (Et 4 L)Cl]. The corresponding reactions of the ligand with [Re(CO) 5 Br] give only the mononuclear analogue, [Re(CO) 3 (Et 4 L)Br]. All the complexes were structurally characterized. The X-ray structure of the dinuclear complex revealed that two facially coordinated {Re(CO) 3 } + moieties are chelated by the novel inner-salt type Sulfur Donor ligand and are bridged by two chloride ligands. The ReCO bonds, trans to the S Donors of the ligand are longer than the other ReCO bonds, evidently due to the strong trans influence of the ligand. IR and 1 H and 13 C NMR data indicate that all the complexes are substantially stable in solution. The dinuclear complex displays metal based and ligand based quasi-reversible oxidation and reduction couples, respectively, whereas the mononuclear complexes are unstable under the same electrochemical conditions.

A. Chandrasekaran - One of the best experts on this subject based on the ideXlab platform.

  • The First Hydrogen Bonded Anionic Phosphates Exhibiting Sulfur Donor Coordination1
    Inorganic Chemistry, 1999
    Co-Authors: A. Chandrasekaran, Paul Sood, Roberta O. Day, Robert R. Holmes
    Abstract:

    We have synthesized and structurally characterized the first anionic phosphates undergoing Sulfur Donor action in the presence of hydrogen bonding. As a consequence, these phosphates increase their coordination geometry toward a trigonal bipyramid. It is suggested that such action may occur at active sites of phosphoryl transfer enzyme containing anionic phosphate substrates.

  • Pentacoordinated Organo and Hydrido Cyclic Silanes via Sulfur Donor Action1
    Organometallics, 1999
    Co-Authors: Ramil-marcelo L. Mercado, A. Chandrasekaran, Roberta O. Day, Robert R. Holmes
    Abstract:

    The new cyclic organosilanes S(C10H6O)2SiMe2 (1) and S(C10H6O)2SiPh2 (2) were obtained by the reaction of R2Si(NMe2)2 (R = Me, Ph) with thiobis(2,2‘-naphthol), while S[Me2C6H2O]2SiH(Me) (3) and S[(t-Bu)MeC6H2O]2SiH(Me) (4) were formed by reaction of Cl2SiH(Me) with the appropriate diol in the presence of Et3N. Characterization was achieved by 29Si and 1H solution NMR, 29Si solid-state NMR, and X-ray structural studies. As a result of Sulfur Donor interaction, pentacoordinate geometries were obtained where 3 and 4 were displaced further toward a trigonal bipyramid (TBP) compared to 1 and 2. Variable-temperature NMR spectra showed 1 to be fluxional with an activation energy of 9.4 kcal/mol. An exchange mechanism involving rupture of the Si−S Donor interaction accompanying a ring pseudorotation is postulated. The less symmetric silanes 3 and 4 do not exchange, as indicated by the 1H NMR data. Comparison of the degree of Si−S Donor interaction of 1−4 with that of related cyclic organosilanes possessing Si−O a...

  • Increased coordination via Sulfur Donor action in cyclic pentaoxyphosphoranes and the parent cyclic phosphite. Influence of pentafluorophenoxy ligands
    Inorganic chemistry, 1998
    Co-Authors: Paul Sood, A. Chandrasekaran, Roberta O. Day, Robert R. Holmes
    Abstract:

    The pentafluorophenoxy ligand was introduced into the new cyclic pentaoxyphosphoranes S[(t-Bu)MeC(6)H(2)O](2)P(OC(6)F(5))(O(2)C(6)Cl(4)) (1), S[(t-Bu)MeC(6)H(2)O](2)P(OC(6)F(5))(O(2)C(14)H(8)) (2), and S[(t-Bu)MeC(6)H(2)O](2)P(OC(6)F(5))(3) (3). X-ray analysis revealed hexacoordinate structures formed by Sulfur Donor action present as a bridging atom in flexible eight-membered rings for 1-3. X-ray analysis showed that Sulfur coordination also occurred with the same type of ring system as part of the phosphite S[(t-Bu)MeC(6)H(2)O](2)P(OC(6)F(5)) (4) to give a pseudo-trigonal-bipyramidal geometry. The pentafluorophenoxy ligand present in the oxyphosphoranes 1-3 as well as in the phosphite 4 acts comparably to a chlorine atom in its ability to enhance phosphorus electrophilicity as measured by the degree of P-S coordination and geometrical displacement toward a more highly coordinated state. The phosphite 4 has a P-S Donor distance of 2.876(2) A, considerably longer than the range of P-S distances from 2.366(3) to 2.495(2) A obtained for the pentaoxyphosphoranes 1-3. These data express quantitatively the relative electrophilicity of phosphorus as a function of coordination number and substituent composition.

  • Hexacoordination via Sulfur Donor Action in Bicyclic Pentaoxyphosphoranes(1).
    Inorganic chemistry, 1997
    Co-Authors: Paul Sood, A. Chandrasekaran, T. K. Prakasha, Roberta O. Day, Robert R. Holmes
    Abstract:

    New bicyclic oxyphosphoranes, S[(t-Bu)MeC(6)H(2)O](2)P(OC(6)H(5))(O(2)C(6)H(3)F) (1) and S[(t-Bu)MeC(6)H(2)O](2)P(OC(6)H(5))(O(2)C(6)H(4)) (3), were synthesized by displacement reactions of a monocyclic pentaoxyphosphorane by a diol, and S[(t-Bu)(2)C(6)H(2)O](2)P(OCH(2)CF(3))(O(2)C(6)Cl(4)) (2) and S[(t-Bu)(2)C(6)H(2)O](2)P(C(6)H(5))(O(2)C(6)Cl(4)) (4), by oxidative addition reactions of a phosphite or phosphine with tetrachlorobenzoquinone. X-ray studies revealed hexacoordinated structures formed by the presence of a Sulfur Donor atom incorporated in a flexible eight-membered ring. The structures were displaced along a coordinate from a square pyramid toward an octahedron. (31)P and (1)H NMR data are also reported. Comparisons are made between bicyclic tetraoxyphosphoranes and monocyclic and bicyclic pentaoxyphosphoranes which show the importance of ligand electronegativity in increasing the degree of hexacoordination. Of the various series now studied, the extent of Sulfur Donor atom coordination increases in the following order: phosphates < phosphites < oxyphosphoranes. It is concluded that, in general, Sulfur Donor atom coordination will take place with phosphorus in any of the common coordination geometries in the presence of sufficiently electronegative ligands.

  • pentacoordination and pseudopentacoordination via Sulfur Donor action in cyclic phosphates and phosphites1
    Inorganic Chemistry, 1997
    Co-Authors: David J Sherlock, A. Chandrasekaran, Roberta O. Day, Robert R. Holmes
    Abstract:

    New cyclic chlorophosphites S[(t-Bu)2C6H2O]2PCl (3) and CH2[(t-Bu)MeC6H2O]2PCl (6) and the cyclic phosphate S[(t-Bu)MeC6H2O]2P(O)Cl (4) were synthesized from the reaction of PCl3 or POCl3 with the ...

Rita Colnaghi - One of the best experts on this subject based on the ideXlab platform.

  • Mutagenic analysis of Thr‐232 in rhodanese from Azotobacter vinelandii highlighted the differences of this prokaryotic enzyme from the known Sulfurtransferases
    FEBS Letters, 2000
    Co-Authors: Silvia Pagani, Aristodemo Carpen, Fabio Forlani, Domenico Bordo, Rita Colnaghi
    Abstract:

    Azotobacter vinelandii RhdA uses thiosulfate as the only Sulfur Donor in vitro, and this apparent selectivity seems to be a unique property among the characterized Sulfurtransferases. To investigate the basis of substrate recognition in RhdA, we replaced Thr-232 with either Ala or Lys. Thr-232 was the target of this study since the corresponding Lys-249 in bovine rhodanese has been identified as necessary for catalytic Sulfur transfer, and replacement of Lys-249 with Ala fully inactivates bovine rhodanese. Both T232K and T232A mutants of RhdA showed significant increase in thiosulfate-cyanide Sulfurtransferase activity, and no detectable activity in the presence of 3-mercaptopyruvate as the Sulfur Donor substrate. Fluorescence measurements showed that wild-type and mutant RhdAs were overexpressed in the perSulfurated form, thus conferring to this enzyme the potential of a persulfide Sulfur Donor compound. RhdA contains a unique sequence stretch around the catalytic cysteine, and the data here presented suggest a possible divergent physiological function of A. vinelandii Sulfurtransferase.

  • Mutagenic analysis of Thr-232 in rhodanese from Azotobacter vinelandii highlighted the differences of this prokaryotic enzyme from the known Sulfurtransferases.
    FEBS Letters, 2000
    Co-Authors: Silvia Pagani, Aristodemo Carpen, Fabio Forlani, Domenico Bordo, Rita Colnaghi
    Abstract:

    Azotobacter vinelandii RhdA uses thiosulfate as the only Sulfur Donor in vitro, and this apparent selectivity seems to be a unique property among the characterized Sulfurtransferases. To investigate the basis of substrate recognition in RhdA, we replaced Thr-232 with either Ala or Lys. Thr-232 was the target of this study since the corresponding Lys-249 in bovine rhodanese has been identified as necessary for catalytic Sulfur transfer, and replacement of Lys-249 with Ala fully inactivates bovine rhodanese. Both T232K and T232A mutants of RhdA showed significant increase in thiosulfate-cyanide Sulfurtransferase activity, and no detectable activity in the presence of 3-mercaptopyruvate as the Sulfur Donor substrate. Fluorescence measurements showed that wild-type and mutant RhdAs were overexpressed in the perSulfurated form, thus conferring to this enzyme the potential of a persulfide Sulfur Donor compound. RhdA contains a unique sequence stretch around the catalytic cysteine, and the data here presented suggest a possible divergent physiological function of A. vinelandii Sulfurtransferase.

Roberta O. Day - One of the best experts on this subject based on the ideXlab platform.

  • The First Hydrogen Bonded Anionic Phosphates Exhibiting Sulfur Donor Coordination1
    Inorganic Chemistry, 1999
    Co-Authors: A. Chandrasekaran, Paul Sood, Roberta O. Day, Robert R. Holmes
    Abstract:

    We have synthesized and structurally characterized the first anionic phosphates undergoing Sulfur Donor action in the presence of hydrogen bonding. As a consequence, these phosphates increase their coordination geometry toward a trigonal bipyramid. It is suggested that such action may occur at active sites of phosphoryl transfer enzyme containing anionic phosphate substrates.

  • Pentacoordinated Organo and Hydrido Cyclic Silanes via Sulfur Donor Action1
    Organometallics, 1999
    Co-Authors: Ramil-marcelo L. Mercado, A. Chandrasekaran, Roberta O. Day, Robert R. Holmes
    Abstract:

    The new cyclic organosilanes S(C10H6O)2SiMe2 (1) and S(C10H6O)2SiPh2 (2) were obtained by the reaction of R2Si(NMe2)2 (R = Me, Ph) with thiobis(2,2‘-naphthol), while S[Me2C6H2O]2SiH(Me) (3) and S[(t-Bu)MeC6H2O]2SiH(Me) (4) were formed by reaction of Cl2SiH(Me) with the appropriate diol in the presence of Et3N. Characterization was achieved by 29Si and 1H solution NMR, 29Si solid-state NMR, and X-ray structural studies. As a result of Sulfur Donor interaction, pentacoordinate geometries were obtained where 3 and 4 were displaced further toward a trigonal bipyramid (TBP) compared to 1 and 2. Variable-temperature NMR spectra showed 1 to be fluxional with an activation energy of 9.4 kcal/mol. An exchange mechanism involving rupture of the Si−S Donor interaction accompanying a ring pseudorotation is postulated. The less symmetric silanes 3 and 4 do not exchange, as indicated by the 1H NMR data. Comparison of the degree of Si−S Donor interaction of 1−4 with that of related cyclic organosilanes possessing Si−O a...

  • Increased coordination via Sulfur Donor action in cyclic pentaoxyphosphoranes and the parent cyclic phosphite. Influence of pentafluorophenoxy ligands
    Inorganic chemistry, 1998
    Co-Authors: Paul Sood, A. Chandrasekaran, Roberta O. Day, Robert R. Holmes
    Abstract:

    The pentafluorophenoxy ligand was introduced into the new cyclic pentaoxyphosphoranes S[(t-Bu)MeC(6)H(2)O](2)P(OC(6)F(5))(O(2)C(6)Cl(4)) (1), S[(t-Bu)MeC(6)H(2)O](2)P(OC(6)F(5))(O(2)C(14)H(8)) (2), and S[(t-Bu)MeC(6)H(2)O](2)P(OC(6)F(5))(3) (3). X-ray analysis revealed hexacoordinate structures formed by Sulfur Donor action present as a bridging atom in flexible eight-membered rings for 1-3. X-ray analysis showed that Sulfur coordination also occurred with the same type of ring system as part of the phosphite S[(t-Bu)MeC(6)H(2)O](2)P(OC(6)F(5)) (4) to give a pseudo-trigonal-bipyramidal geometry. The pentafluorophenoxy ligand present in the oxyphosphoranes 1-3 as well as in the phosphite 4 acts comparably to a chlorine atom in its ability to enhance phosphorus electrophilicity as measured by the degree of P-S coordination and geometrical displacement toward a more highly coordinated state. The phosphite 4 has a P-S Donor distance of 2.876(2) A, considerably longer than the range of P-S distances from 2.366(3) to 2.495(2) A obtained for the pentaoxyphosphoranes 1-3. These data express quantitatively the relative electrophilicity of phosphorus as a function of coordination number and substituent composition.

  • Hexacoordination via Sulfur Donor Action in Bicyclic Pentaoxyphosphoranes(1).
    Inorganic chemistry, 1997
    Co-Authors: Paul Sood, A. Chandrasekaran, T. K. Prakasha, Roberta O. Day, Robert R. Holmes
    Abstract:

    New bicyclic oxyphosphoranes, S[(t-Bu)MeC(6)H(2)O](2)P(OC(6)H(5))(O(2)C(6)H(3)F) (1) and S[(t-Bu)MeC(6)H(2)O](2)P(OC(6)H(5))(O(2)C(6)H(4)) (3), were synthesized by displacement reactions of a monocyclic pentaoxyphosphorane by a diol, and S[(t-Bu)(2)C(6)H(2)O](2)P(OCH(2)CF(3))(O(2)C(6)Cl(4)) (2) and S[(t-Bu)(2)C(6)H(2)O](2)P(C(6)H(5))(O(2)C(6)Cl(4)) (4), by oxidative addition reactions of a phosphite or phosphine with tetrachlorobenzoquinone. X-ray studies revealed hexacoordinated structures formed by the presence of a Sulfur Donor atom incorporated in a flexible eight-membered ring. The structures were displaced along a coordinate from a square pyramid toward an octahedron. (31)P and (1)H NMR data are also reported. Comparisons are made between bicyclic tetraoxyphosphoranes and monocyclic and bicyclic pentaoxyphosphoranes which show the importance of ligand electronegativity in increasing the degree of hexacoordination. Of the various series now studied, the extent of Sulfur Donor atom coordination increases in the following order: phosphates < phosphites < oxyphosphoranes. It is concluded that, in general, Sulfur Donor atom coordination will take place with phosphorus in any of the common coordination geometries in the presence of sufficiently electronegative ligands.

  • pentacoordination and pseudopentacoordination via Sulfur Donor action in cyclic phosphates and phosphites1
    Inorganic Chemistry, 1997
    Co-Authors: David J Sherlock, A. Chandrasekaran, Roberta O. Day, Robert R. Holmes
    Abstract:

    New cyclic chlorophosphites S[(t-Bu)2C6H2O]2PCl (3) and CH2[(t-Bu)MeC6H2O]2PCl (6) and the cyclic phosphate S[(t-Bu)MeC6H2O]2P(O)Cl (4) were synthesized from the reaction of PCl3 or POCl3 with the ...

Related terms

Sulfur Donor - 15 days free trial to Access Experts & Abstracts