Abstract:(Pentane-2,4-dionato)-tetrafluorophosphorane crystallises in the space group P21/c, Z = 8, with a = 8.896(2), b = 13.760(4), c = 13.316(2) Å, β = 93.42(3)°. The structure was refined to R = 0.053 for 2445 reflections. Small but significant differences are observed in the bond angles at phosphorus and in the chelate ring conformations of the two independent molecules. These display an approximate mirror plane perpendicular to the chelate rings, which are in the boat form with P and… Show more
“…The compound was shown to have a comparable physical nature to other main-group and metallic β-diketonates. Twelve years later, the X-ray crystal structure of (acetylacetonato)tetrafluorophosphorus(V) ( 39 ) was reported (Figure ) which confirmed the earlier structural conclusions. Noteworthy features of the structure include an approximate plane of symmetry perpendicular to the six-membered ring.…”
“…The compound was shown to have a comparable physical nature to other maingroup and metallic β-diketonates. Twelve years later, the X-ray crystal structure of (acetylacetonato)tetrafluorophosphorus(V) (39) was reported (Figure 23) 99 100 Although geometrical isomers could exist for all the compounds, only F 3 (CF 3 )P(acac) (40a) shows more than one specific structural isomer in the NMR spectra corresponding to axial or radial CF 3 position in the compound (axial : radial isomer distribution ca. 1:2).…”
“…The compound was shown to have a comparable physical nature to other main-group and metallic β-diketonates. Twelve years later, the X-ray crystal structure of (acetylacetonato)tetrafluorophosphorus(V) ( 39 ) was reported (Figure ) which confirmed the earlier structural conclusions. Noteworthy features of the structure include an approximate plane of symmetry perpendicular to the six-membered ring.…”
“…The compound was shown to have a comparable physical nature to other maingroup and metallic β-diketonates. Twelve years later, the X-ray crystal structure of (acetylacetonato)tetrafluorophosphorus(V) (39) was reported (Figure 23) 99 100 Although geometrical isomers could exist for all the compounds, only F 3 (CF 3 )P(acac) (40a) shows more than one specific structural isomer in the NMR spectra corresponding to axial or radial CF 3 position in the compound (axial : radial isomer distribution ca. 1:2).…”
“…The structures of hexacoordinated phosphorus exhibiting cationic and anionic formulations as well as additional neutral species with oxygen and nitrogen ligands also are known, e.g ., 6 − 14 (Chart ). − 1 …”
Section: Structural Characterizationmentioning
confidence: 99%
“…The structures of hexacoordinated phosphorus exhibiting cationic and anionic formulations as well as additional neutral species with oxygen and nitrogen ligands also are known, e.g., 6-14 (Chart 1). [57][58][59][60][61][62][63][64][65][66] However, only recently have structural studies revealed sulfur capable of inducing hexacoordination for phosphorus. This aspect is discussed in the next section.…”
Section: Via Nitrogen and Oxygen Donationmentioning
as Professor of Inorganic Chemistry. His publications number over 200 and include two invited ACS monographs, Nos. 175 and 176, on pentacoordinated phosphorus. His wife, Joan, is a chemist who is a coauthor on many of his publications. Currently, he is Editor-in-Chief of Phosphorus, Sulfur, and Silicon and the Related Elements and Consultant Editor of Main Group Chemistry News.
“…Other examples of hexacoordinated phosphorus are known that are formed as a result of donor action from more electronegative nitrogen and oxygen containing ligands, , e.g ., C and D . In all of these, the ligands attached to phosphorus collectively provide a high degree of electronegativity.…”
Oxidative addition reactions of a quinone with the sulfur
containing cyclic chlorophosphine
S[(t-Bu)MeC6H2O]2PCl (1)
yielded the new bicyclic tetraoxyphosphoranes,
S[(t-Bu)MeC6H2O]2PCl(O2C6Cl4)
(2) and S[(t-Bu)MeC6H2O]2PCl(O2C14H8)
(5). Further new derivatives of this class were
prepared by chlorine displacement
reactions of 2 and 5 to give
S[(t-Bu)MeC6H2O]2P(NHC6H4Me)(O2C6Cl4)
(3),
S[(t-Bu)MeC6H2O]2P(NMe2)(O2C6Cl4)
(4),
S[(t-Bu)MeC6H2O]2P(NHCH2C6H5)(O2C14H8)
(6), and
S[(t-Bu)MeC6H2O]2P(NMe2)(O2C14H8)
(7). X-ray studies
of 2−6 revealed hexacoordination due to donor
action by sulfur which is present as part of an eight-membered
ring
system. The series 2−6 formed geometries
that were displaced along a coordinate from a square pyramid to
an
octahedron, ranging from 24% to 71%. The respective P−S
distance decreased along this series from 3.04 to 2.48
Å as the octahedral character increased. Increased
31P NMR shielding accompanied the chloro derivatives
2 and 5,
while increased π P−N back-bonding resulted in the least shielded
members 4, 6, and 7 containing the
less
electronegative nitrogen atom. These changes in 31P
chemical shift correlate with the extent of octahedral
character
where the more shielded phosphorus atom has the greater octahedral
character. The analysis allows a lower limit in
the phosphorus atom electrophilicity to be established that will allow
hexacoordination in this series of bicyclic
tetraoxyphosphoranes provided by a variation in ligand
properties.
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