Effects of carbon chain substituents on the P⋯N noncovalent bond

Abstract The effects of carbon chains placed on the electron-accepting P atom of a P⋯N bond are examined via ab initio calculations. Saturated alkyl groups have a mild weakening effect, regardless of chain length. In contrast, incorporation of double bonds into the chain strengthens the interaction, C C triple bonds even more so. These effects are only slightly enhanced by additional conjugated double bonds or an aromatic ring. Placing F atoms onto the carbon chains strengthens the P⋯N bond, but only by a small amount, which wanes as the F atom is displaced further from the P along the chain.

[1]  S. Scheiner,et al.  Comparison of P···D (D = P,N) with other noncovalent bonds in molecular aggregates. , 2011, The Journal of chemical physics.

[2]  M. Chudziński,et al.  Anion receptors composed of hydrogen- and halogen-bond donor groups: modulating selectivity with combinations of distinct noncovalent interactions. , 2011, Journal of the American Chemical Society.

[3]  M. Bühl,et al.  Prediction of a new delocalised bonding motif between group 15 or group 16 atoms. , 2011, Chemphyschem : a European journal of chemical physics and physical chemistry.

[4]  Barbara Kirchner,et al.  Pnicogen bonds: a new molecular linker? , 2011, Chemistry.

[5]  G. Gilli,et al.  The Nature of the Hydrogen Bond , 2009 .

[6]  D. Werz,et al.  Nanotube formation favored by chalcogen-chalcogen interactions. , 2002, Journal of the American Chemical Society.

[7]  Pavel Hobza,et al.  On the nature of the stabilization of benzene···dihalogen and benzene···dinitrogen complexes: CCSD(T)/CBS and DFT-SAPT calculations. , 2011, Chemphyschem : a European journal of chemical physics and physical chemistry.

[8]  N. Walker,et al.  Molecular geometries of H2S···ICF3 and H2O···ICF3 characterised by broadband rotational spectroscopy. , 2011, Physical chemistry chemical physics : PCCP.

[9]  Shuji Tomoda,et al.  Statistical and theoretical investigations on the directionality of nonbonded S...O interactions. Implications for molecular design and protein engineering. , 2002, Journal of the American Chemical Society.

[10]  M. Balakrishna,et al.  Weak interactions between trivalent pnictogen centers: computational analysis of bonding in dimers X3E...EX3 (E = pnictogen, X = halogen). , 2009, Inorganic chemistry.

[11]  Steve Scheiner,et al.  A new noncovalent force: comparison of P···N interaction with hydrogen and halogen bonds. , 2011, The Journal of chemical physics.

[12]  José Elguero,et al.  Charge-Transfer Complexes between Dihalogen Compounds and Electron Donors , 1998 .

[13]  Qingzhong Li,et al.  Competition of chalcogen bond, halogen bond, and hydrogen bond in SCSHOX and SeCSeHOX (X = Cl and Br) complexes , 2012 .

[14]  F. Temple Burling,et al.  Computational studies of nonbonded sulfur-oxygen and selenium-oxygen interactions in the thiazole and selenazole nucleosides , 1992 .

[15]  Steve Scheiner,et al.  Effects of substituents upon the P···N noncovalent interaction: the limits of its strength. , 2011, The journal of physical chemistry. A.

[16]  Qiang Zhao,et al.  Theoretical investigations on the weak nonbonded CS···CH2 interactions: Chalcogen‐bonded complexes with singlet carbene as an electron donor , 2011 .

[17]  P. Metrangolo,et al.  Halogen Versus Hydrogen , 2008, Science.

[18]  L. Curtiss,et al.  Intermolecular interactions from a natural bond orbital, donor-acceptor viewpoint , 1988 .

[19]  Y. Nagao,et al.  Intramolecular Nonbonded S···O Interaction Recognized in (Acylimino)thiadiazoline Derivatives as Angiotensin II Receptor Antagonists and Related Compounds , 1998 .

[20]  L. Evangelisti,et al.  On the Cl···N halogen bond: a rotational study of CF3Cl···NH3. , 2012, Chemistry.

[21]  Professor Dr. George A. Jeffrey,et al.  Hydrogen Bonding in Biological Structures , 1991, Springer Berlin Heidelberg.

[22]  Jindřich Fanfrlík,et al.  Halogen bond tunability I: the effects of aromatic fluorine substitution on the strengths of halogen-bonding interactions involving chlorine, bromine, and iodine , 2011, Journal of molecular modeling.

[23]  Horst Köppel,et al.  Theoretical investigations on chalcogen-chalcogen interactions: what makes these nonbonded interactions bonding? , 2006, Journal of the American Chemical Society.

[24]  J. Murray,et al.  σ-hole bonding: molecules containing group VI atoms , 2007 .

[25]  Jianji Wang,et al.  Density functional study of AgnPd and AgnPdH clusters , 2011 .

[26]  José Elguero,et al.  31P–31P spin–spin coupling constants for pnicogen homodimers , 2011 .

[27]  S. B. Bushuk,et al.  Hypercoordinate silicon and phosphorus acetylene compounds: crystal structure determinations and fluorescence spectroscopic study , 2004 .

[28]  A. Slawin,et al.  Synthetic and structural studies of 1,8-chalcogen naphthalene derivatives. , 2010, Chemistry.

[29]  M. Waugh,et al.  The interaction of phosphavinyl Grignard reagents with group 15 halides: synthesis and structural characterisation of novel heterocyclic and heterocage compounds , 2002 .

[30]  Steve Scheiner,et al.  Effects of Multiple Substitution upon the P∙∙∙N Noncovalent Interaction , 2011 .

[31]  O. Hassel,et al.  Structural aspects of interatomic charge-transfer bonding. , 1970, Science.

[32]  W. Herrebout,et al.  Halogen bonding to a divalent sulfur atom: an experimental study of the interactions of CF3X (X = Cl, Br, I) with dimethyl sulfide. , 2011, Physical chemistry chemical physics : PCCP.

[33]  José Elguero,et al.  Structures, energies, bonding, and NMR properties of pnicogen complexes H2XP:NXH2 (X ═ H, CH3, NH2, OH, F, Cl). , 2011, The journal of physical chemistry. A.

[34]  Frank H. Allen,et al.  The Nature and Geometry of Intermolecular Interactions between Halogens and Oxygen or Nitrogen , 1996 .

[35]  Xiaoyan Li,et al.  Ab initio and AIM studies on typical π‐type and pseudo‐π‐type halogen bonds: Comparison with hydrogen bonds , 2011 .

[36]  J. Dunitz,et al.  Directional preferences of nonbonded atomic contacts with divalent sulfur. 1. Electrophiles and nucleophiles , 1977 .

[37]  Peter Politzer,et al.  σ‐Hole bonding and hydrogen bonding: Competitive interactions , 2007 .

[38]  Frank Weinhold,et al.  Natural bond orbital analysis of molecular interactions: Theoretical studies of binary complexes of , 1986 .

[39]  J. Novoa,et al.  Theoretical evaluation of the nature and strength of the F···F intermolecular interactions present in fluorinated hydrocarbons , 2011 .

[40]  W. Herrebout,et al.  C-X···π halogen and C-H···π hydrogen bonding: interactions of CF3X (X = Cl, Br, I or H) with ethene and propene. , 2012, Physical chemistry chemical physics : PCCP.

[41]  Steve Scheiner,et al.  Hydrogen Bonding: A Theoretical Perspective , 1997 .

[42]  S. F. Boys,et al.  The calculation of small molecular interactions by the differences of separate total energies. Some procedures with reduced errors , 1970 .

[43]  S. Scheiner.  On the properties of X···N noncovalent interactions for first-, second-, and third-row X atoms. , 2011, The Journal of chemical physics.

[44]  S. Scheiner.  Can two trivalent N atoms engage in a direct N⋯N noncovalent interaction? , 2011 .

[45]  Timothy Clark,et al.  Halogen bonding: the σ-hole , 2007 .