TY - JOUR
T1 - Charge-shift bonding and its manifestations in chemistry
AU - Shaik, Sason
AU - Danovich, David
AU - Wu, Wei
AU - Hiberty, Philippe C.
PY - 2009/9
Y1 - 2009/9
N2 - Electron-pair bonding is a central chemical paradigm. Here, we show that alongside the two classical covalent and ionic bond families, there exists a class of charge-shift (CS) bonds wherein the electron-pair fluctuation has the dominant role. Charge-shift bonding shows large covalent-ionic resonance interaction energy, and depleted charge densities, and features typical to repulsive interactions, albeit the bond itself may well be strong. This bonding type is rooted in a mechanism whereby the bond achieves equilibrium defined by the virial ratio. The CS bonding territory involves, for example, homopolar bonds of compact electronegative and/or lone-pair-rich elements, heteropolar bonds of these elements among themselves and with other atoms (for example, the metalloids, such as silicon and germanium), hypercoordinated molecules, and bonds whose covalent components are weakened by exchange-repulsion strain (as in [1.1.1]propellane). Here, we discuss experimental manifestations of CS bonding in chemistry, and outline new directions demonstrating the portability of the new concept.
AB - Electron-pair bonding is a central chemical paradigm. Here, we show that alongside the two classical covalent and ionic bond families, there exists a class of charge-shift (CS) bonds wherein the electron-pair fluctuation has the dominant role. Charge-shift bonding shows large covalent-ionic resonance interaction energy, and depleted charge densities, and features typical to repulsive interactions, albeit the bond itself may well be strong. This bonding type is rooted in a mechanism whereby the bond achieves equilibrium defined by the virial ratio. The CS bonding territory involves, for example, homopolar bonds of compact electronegative and/or lone-pair-rich elements, heteropolar bonds of these elements among themselves and with other atoms (for example, the metalloids, such as silicon and germanium), hypercoordinated molecules, and bonds whose covalent components are weakened by exchange-repulsion strain (as in [1.1.1]propellane). Here, we discuss experimental manifestations of CS bonding in chemistry, and outline new directions demonstrating the portability of the new concept.
UR - http://www.scopus.com/inward/record.url?scp=69249209772&partnerID=8YFLogxK
U2 - 10.1038/nchem.327
DO - 10.1038/nchem.327
M3 - ???researchoutput.researchoutputtypes.contributiontojournal.article???
C2 - 21378912
AN - SCOPUS:69249209772
SN - 1755-4330
VL - 1
SP - 443
EP - 449
JO - Nature Chemistry
JF - Nature Chemistry
IS - 6
ER -