Formation of a phosphine-phosphinite ligand in RhCl(PRR′2) [P,P-R′(R)POCH2P(CH2OH)2] and R′H from cis-RhCl(PRR′2)2[P(CH2OH) 3] via P-C bond cleavage

Article abstract of DOI:10.1021/ic7012182

Reaction of RhCl(1,5-cod)(THP), where THP = P(CH₂OH) ₃, with several PRR′₂ phosphines (R = or ≠ R′) generates, concomitantly with R′H, the derivatives RhCl(PRR′₂)[P,P-R′(R)POCH₂P(CH ₂OH)₂] in two isomeric forms. The hydrogen of the hydrocarbon co-product derives from a THP hydroxyl group which becomes an 'alkoxy' group at the residual PRR' moiety, this resulting in the P,P-chelated R′(R)POCH₂P(CH₂OH)₂ ligand. One of the isomers of the PPh₃ system, cis-RhCl(PPh₃)[P, P-P(Ph) ₂OCH₂P(CH₂OH)₂], was structurally characterized (cis refers to the disposition of the P atoms with Ph substituents).

Full text of DOI:10.1021/ic7012182

Inorg. Chem. 2007, 46, 8998−9002
Formation of a Phosphine
RhCl(PRR 2)[P,P-R (R)POCH2P(CH2OH)2] and R
cis-RhCl(PRR 2)2[P(CH2OH)3] via P C Bond Cleavage
−phosphinite Ligand in
′
′
′
H from
′
−
Fabio Lorenzini, Brian O. Patrick, and Brian R. James*
Department of Chemistry, The UniVersity of British Columbia, VancouVer,
British Columbia, Canada, V6T 1Z1
Received June 21, 2007
Reaction of RhCl(1,5-cod)(THP), where THP
concomitantly with R H, the derivatives RhCl(PRR
of the hydrocarbon co-product derives from a THP hydroxyl group which becomes an ‘alkoxy’ group at the residual
PRR moiety, this resulting in the P,P-chelated R (R)POCH2P(CH2OH)2 ligand. One of the isomers of the PPh3
)
P(CH2OH)3, with several PRR′2 phosphines (R ) or * R′) generates,
′
′
2)[P,P-R (R)POCH2P(CH2OH)2] in two isomeric forms. The hydrogen
′
′
′
system, cis-RhCl(PPh3)[P,P-P(Ph)2OCH2P(CH2OH)2], was structurally characterized (cis refers to the disposition of
the P atoms with Ph substituents).
Scheme 1. Synthesis of cis- and trans-
RhCl(PRR′2)[P,P-R′(R)POCH2P(CH2OH)2]
Introduction
We have recently reported the syntheses of water-soluble
RhI-THP complexes (THP is tris(hydroxymethyl)phosphine
[P(CH2OH)3]),1 which have potential in the areas of aqueous
or aqueous/organic two-phase homogeneous catalysis2 and
in biomedical applications using water-soluble drugs.3 During
a subsequent study of the general reactivity of the complexes
with other potential ligands, we have discovered a remarkable
reaction of RhCl(cod)(THP) (1, cod ) 1,5-cyclooctadiene)1
with PRR′2 tertiary phosphines (R ) or * R′). Initially
formed rapidly is the cis-RhCl(PRR′2)2(THP) species (2,
detected for the PPh3 and P(p-F-C6H4)3 systems), but this
slowly converts via a THP-promoted P-C bond cleavage
of one of the two PRR′2 ligands to give two isomers of RhCl-
(PRR′2)[P,P-R′(R)POCH2P(CH2OH)2] (for example: 3, R
) R′ ) Ph; 4, R ) cyclohexyl, R′ ) Ph) and the hydrocarbon
co-product R′H for which a THP-hydroxy proton provides
the hydrogen; the new P,P-R′(R)POCH2P(CH2OH)2 chelat-
ing phosphine-phosphinite ligand contains an ‘alkoxy’
residue at the residual PRR′ moiety (see Scheme 1). Reaction
of 1 with PPh3 provided evidence for intermediate 2 and
gave a crystal of 3 that was characterized by X-ray analysis,
while the corresponding reaction of 1 with PCyPh2 (where
Cy ) cyclohexyl) to give 4, in conjunction with the structural
data, allowed for analysis of the 31P{1H} NMR data.
Experimental Section
General. The RhCl(cod)(THP) complex (1) was synthesized by
our recently reported method;1 the phosphines were used as received
from Strem Chemicals, and the reactions with the Rh complex were
carried out under Ar using standard Schlenk techniques or in a
J-Young NMR tube. MeOH was dried over Mg-I2, and distilled
under N2. 31P{1H}, 13C{1H}, and 1H NMR spectra were measured
in CD3OD at room temperature (∼300 K), unless stated otherwise,
on a Bruker AV400 spectrometer. A residual deuterated solvent
proton (relative to external SiMe4) and external 85% aq H3PO4 were
used as references (d ) doublet, m ) multiplet; J values given in
Hz). Elemental analyses were performed on a Carlo Erba 1108
* To whom correspondence should be addressed. E-mail:brj@chem.ubc.ca.
(1) Lorenzini, F.; Patrick, B. O.; James, B. R. Dalton Trans. 2007, 3224.
(2) Wiebus E.; Cornils, B. In Catalyst Separation, RecoVery and Recycling;
Cole-Hamilton, D., Tooze, R., Eds.; Springer: Dordrecht, 2006;
Chapter 5.
(3) (a) Raghuraman, K.; Pillarsetty, N.; Volkert, W. A.; Barnes, C.;
Jurisson, S.; Katti, K. V. J. Am. Chem. Soc. 2002, 124, 7276. (b)
Jurisson, S. S.; Ketring, A. R.; Volkert, W. A. Transition Met. Chem.
1997, 22, 315.
8998 Inorganic Chemistry, Vol. 46, No. 21, 2007
10.1021/ic7012182 CCC: $37.00
© 2007 American Chemical Society
Published on Web 09/15/2007

Formation of a Phosphine-Phosphinate Ligand
analyzer. Mass spectrometry was performed on a Bruker Esquire
electrospray (ESI) ion-trap spectrometer with samples dissolved in
MeOH, with positive-ion polarity scanning from 60 to 1000 m/z.
GC (HP-17 capillary column, 25 m × 0.25 mm (0.26 µm film),
50 °C for 20 min): tR ) 1.20 min (benzene). GCMS (Agilent
Technologies; 6890N Network GC System, 5975B Inert MSD; HP-
chiral column, 30 m × 0.25 mm (0.25 µm film), 50 °C for 20
min): tR 2.25 min, M ) 79 (benzene-d1).
cis- and trans-RhCl(PPh3)[P,P-P(Ph)2OCH2P(CH2OH)2] (3).
Addition of PPh3 (15 mg, 0.058 mmol) in MeOH or CH3COCH3
(0.5 mL) to a yellow MeOH or CH3COCH3 solution (0.5 mL) of
1 (10 mg, 0.027 mmol) at room-temperature results in the immediate
formation of a brown solution, but over ∼12 h, the solution becomes
yellow and, after ∼2 weeks, X-ray quality yellow crystals (13 mg,
70% yield) of the cis isomer were deposited from a methanol
1
solution. The 31P{1H} and H NMR spectra of this system were
monitored in CD3OD (see Results and Discussion), while the NMR
spectra of the isolated material are given here. A satisfactory
elemental analysis for 3 was not obtained even for the crystal (see
Figure 1. Structure of cis-RhCl(PPh3)[P,P-P(Ph)2OCH2P(CH2OH)2] (3)‚
2CH3OH, with 50% probability ellipsoids. Selected distances (Å) and angles
(deg): Rh(1)-P(1), 2.2174(6); Rh(1)-P(2), 2.1487(6); Rh(1)-P(3), 2.3205-
(6); Rh(1)-Cl(1), 2.4054(6); P(1)-Rh(1)-P(2), 83.37(2); P(1)-Rh(1)-
P(3), 175.04(2); P(1)-Rh(1)-Cl(1), 87.56(2); P(2)-Rh(1)-P(3), 100.62(2);
P(2)-Rh(1)-Cl(1), 170.93(2); P(3)-Rh(1)-Cl(1), 88.44(2).
1
Results and Discussion). Mass spectrum: 673 (M+). H NMR: δ
3.41-4.28 (m, 6 H, POCH2P(CH2OH)2), 6.95-7.60 (m, 25 H,
C6H5). 13C{1H} NMR: δ 54.51-58.92 (m, POCH2P(CH2OH)2),
129.34-137.38 (m, C6H5). 31P{1H} NMR (see Figure 2 for
labeling): δ 29.62 (m, PRPh3, PAPh3, cis- and trans-3), 68.70 (ddd,
were solved by direct methods.6 Crystallographic data: C35H41O5P3-
RhCl, MW ) 772.95, triclinic, P1h (No. 2), a ) 10.472(1) Å, b )
11.607(1) Å, c ) 14.588(2) Å, R ) 87.553(6)°, â ) 78.799(5)°, γ
) 83.749(5)°, V ) 1728.6(3) Å,3 T ) 173.0(1) K, Z ) 2, µ(Mo
KR) ) 7.51 cm-1, 8381 independent reflections measured, Dcalcd
) 1.485 g cm-3, R1 ) 0.051, wR2 ) 0.068 (for I > 2σ(I)), and
424 refined parameters. CCDC No. 651551.
PB(CH2OH)2 of trans-3, JPBRh = 130.5, JPBPA = 32.6, JPBPC
321.4), and 68.98 (ddd, Pâ(CH2OH)2 of cis-3, JPâRh = 130.5, JPâPR
= 32.6, JPâPγ = 321.4), 170.47 (ddd, Ph2PCO of trans-3, JPCRh
=
=
147.7, JPCPA = 33.3, JPCPB = 321.4), 170.67 (ddd, Ph2PγO of cis-3,
JPγRh = 147.7, JPγPR = 33.3, JPγPâ = 321.4).
cis- and trans-RhCl(PCyPh2)[P,P-Ph(Cy)POCH2P(CH2OH)2]
(4). The reaction of 1 with PCyPh2 was carried out under conditions
identical to those given above for the PPh3 system, and the system
was again monitored by NMR spectroscopy. Maintaining the 12 h
reacted solution at ∼ -18 °C for ∼1 week again deposited yellow
crystals (15 mg, 78% yield), but these were too small for successful
X-ray analysis. Anal. Calcd for C33H45ClO3P3Rh: C, 54.97; H, 6.29.
Results and Discussion
The room-temperature reaction of the yellow complex 1
with PPh3 in MeOH is summarized in Scheme 1. The
immediately formed brown solution by 31P{1H} and 1H NMR
spectra shows loss of 1 (δP 17.7, d, JRhP ) 145), essentially
complete formation of an intermediate, 2, free cod, and trace
amounts of free PPh3 (δP -4.30, s), free THP (δP -25.0, s),
and RhCl(cod)(PPh3) (δP 31.9, d, JRhP ) 150).7 Species 2 is
characterized by three doublets of doublets of doublets for
1
Found: C, 54.74; H, 6.59. Mass spectrum: 686 (M+). H NMR:
δ 0.49-1.56 (m, 22 H, C6H11), 3.07-4.18 (m, 6 H, POCH2P(CH2-
OH)2), 6.99-7.67 (m, 15 H, C6H5). 13C{1H} NMR: δ 26.20-36.35
(m, C6H11), 57.51-60.80 (m, POCH2P(CH2OH)2), 128.44-135.98
(m, C6H5). 31P{1H} NMR (Figure 2): cis-4, δ 28.94 (ddd, PR, JPRRh
) 132.3, JPRPâ ) 292.0, JPRPγ ) 26.4), 82.25 (ddd, Pâ, JPâRh
)
the three inequivalent P atoms: δ 20.07 (Pa(THP), JPaRh
)
139.3, JPâPR ) 292.0, JPâPγ ) 32.1), 196.02 (Pγ, JPγRh ) 199.2,
JPγPR ) 26.4, JPγPâ ) 32.1); trans-4, δ 29.83 (PA, JPARh ) 120.5,
142.2, JPaPb ) 321.4, JPaPc ) 38.6),8 34.88 (PbPh3 trans to
THP, JPbRh ) 130.5, JPbPa ) 321.4, JPbPc ) 38.6), and 50.89
(PcPh3 trans to Cl, JPcRh ) 192.9, JPcPa ) 38.6, JPcPb ) 38.6).
The 31P{1H} spectrum changes over ∼12 h (as the solution
becomes yellow) to one unresolved multiplet at δ 29.62, and
ddd patterns at δ 68.70 and 68.98 and at δ 170.47 and 170.67,
the spectrum being essentially unchanged down to 213 K.
After consideration of the corresponding spectrum for the
PCyPh2 system (see below), these resonances result from a
roughly 1:1 mixture of cis- and trans-3, each isomer having
three inequivalent P atoms; some of the J values for the δ
29.62 resonance can be retrieved from the other two reso-
nances (see Experimental Section, and Tables S1 and S2).
JPAPB ) 33.7, JPAPC ) 352.3), 78.60 (PB, JPBRh ) 180.8, JPBPA
)
33.7, JPBPC ) 34.6), 184.36 (PC, JPCRh ) 148.0, JPCPA ) 352.3, JPCPB
) 34.6).
Other Phosphine Systems. The in situ reactions (under condi-
tions identical to those described above) of 1 with PEtPh2, PMePh2,
P(p-tol)3, P(p-F-C6H4)3, and PnPr3 were monitored by NMR as for
the PPh3 and PCyPh2 systems. No solid complexes were isolated;
the δH and δP shift values and J values for all the systems are in
Tables S1 and S2, respectively, in the Supporting Information.
X-ray Crystallographic Analysis of cis-3. Measurements were
made on a Bruker X8 APEX diffractometer using graphite-
monochromated Mo KR radiation (λ ) 0.71073 Å); data were
collected and integrated using the Bruker SAINT software package4
and were corrected for absorption effects using the multiscan
technique (SADABS),5 with minimum and maximum transmission
coefficients of 0.770 and 0.942, respectively. The data were
corrected for Lorentz and polarization effects, and the structures
(5) SADABS. Bruker Nonius area detector scaling and absorption
correction, V2.10; Bruker AXS Inc.: Madison, WI, 2003.
(6) Altomare, A.; Burla, M. C.; Camalli, M.; Cascarano, G. L.; Giaco-
vazzo, C.; Guagliardi, A.; Moliterni, A. G. G.; Polidori, G.; Spagna,
R. J. Appl. Crystallogr. 1999, 32, 115.
(7) Elsevier, C. J.; Kowall, B.; Kragten, H. Inorg. Chem. 1995, 34, 4836.
(8) Assignment of δ 20.07 to the THP ligand is based on data from ref 1.
(4) SAINT, Version 7.03A; Bruker AXS Inc.: Madison, WI, 1997-2003.
Inorganic Chemistry, Vol. 46, No. 21, 2007 8999

Lorenzini et al.
Figure 2. 31P{1H} NMR spectrum of cis- and trans-RhCl(PCyPh2)[P,P-Ph(Cy)POCH2P(CH2OH)2] (4) (cis/trans ) 1:4).
The key to elucidating the chemistry resulted from slow
precipitation (after 2 weeks) of X-ray quality, yellow crystals.
The crystallographic analysis revealed that the structure was
that of cis-3, the asymmetric unit containing two CH3OH
solvate molecules (Figure 1); cis refers to the disposition of
the P atoms with Ph substituents. The structure revealed that
P-C bond cleavage of a P-C6H5 moiety had occurred and
a -CH2OH of the THP had been converted to an alkoxy
moiety that had replaced the Ph group (Scheme 1); the C6H6
co-product was detected quantitatively by GC and, when the
reaction was carried out in CD3OD, which resulted in D/H
exchange with the hydroxyl protons of THP, C6H5D was
detected by GCMS. Thus, the square planar RhI complex
contains the novel, P,P-chelating phosphine-phosphinite
Ph2POCH2P(CH2OH)2 ligand, with the metal being 0.030-
(5) Å out of the mean plane. Within the asymmetric unit,
there are 12 intermolecular O- -H bonds, which are common
within RhI-THP complexes.1 There are three strong H-bonds
(O- -H ) 1.71-1.73 Å) between the hydroxyl-hydrogen of
a P(CH2OH) and the O atom of CH3OH, one strong H-bond
(O- -H ) 1.78 Å) between an O atom of a P(CH2OH) and
the hydroxyl-hydrogen of CH3OH, and eight weaker H-bonds
(O- -H ) 2.53-2.62 Å): two between the m-H-atom of a
Ph and the O atom of P(CH2OH), two between the p-H-
atom of a Ph and the O atom of CH3OH, two between the
H atom of a P(CH2OH)-methylene and the O atom of CH3-
OH, and two between the H atom of the PCH2OP methylene
and the O atom of CH3OH. The 31P{1H} spectrum of a
methanol solution of the crystal still revealed a 1:1 mixture
of cis- and trans-3, implying rapid equilibrium between the
two isomers in solution, and the independence of the isomer
ratio with temperature implies a thermoneutral equilibrium,
which seems reasonable for the very similar isomeric
structures. The 31P{1H} and 1H NMR spectra show that the
1:1 mixture is indefinitely stable in solution under Ar. An
unsatisfactory elemental analysis for 3 is thought, based on
31P{1H} data, which sometimes showed trace doublet peaks
at δ 31.9 (J ) 150) and 27.9 (J ) 127), to be due to the
presence of traces of RhCl(cod)(PPh3)7 and trans-RhCl(CO)-
(PPh3)2;9 the carbonyl ligand could arise via decarbonylation
of formaldehyde which can be readily formed from transition
metal-THP species.10
The corresponding reaction of PCyPh2 is qualitatively the
same as that with PPh3, the immediately formed brown
solution showing no 31P{1H} signal for 1, some free PCyPh2
(δ -3.03) and a complicated mixture of products showing
δ values between 20.23 and 66.67, but we were unable to
detect the intermediate cis-RhCl(PCyPh2)2(THP), analogous
to that seen in the PPh3 system. The 31P{1H} NMR spectrum
changes over ∼10 h to one showing just two sets of three
(9) O’Connor, J. M.; Ma, J. Inorg. Chem. 1993, 32, 1866.
(10) (a) Higham, L. J.; Whittlesey, M. K.; Wood, P. T. J. Chem. Soc. Dalton
Trans. 2004, 4202. (b) Hoye, P. A. T.; Pringle, P. G.; Smith M. B.;
Worboys, K. J. Chem. Soc. Dalton Trans. 1993, 269.
9000 Inorganic Chemistry, Vol. 46, No. 21, 2007

Formation of a Phosphine-Phosphinate Ligand
doublets of doublets of doublets due to cis- and trans-4
(Scheme 1, Figure 2, and Tables S1 and S2); these species
were readily identified because the cis/trans ratio was now
1:4. Benzene was again formed over the 10 h reaction time.
The 31P{1H} assignments are consistent with literature data:
formation of the five-membered ring and the electron-
withdrawing effect of the O atom bound to Pγ (in cis-4) and
PC (in trans-4) atoms result in the very low-field signals for
these P atoms,11 while the large JPRPâ and JPAPC coupling
constants define the mutually trans positions of these P atoms,
and the 1JRhP values are in the normal range.12 The 1H NMR
signals in CD3OD for the inequivalent methylene protons
of the reactant THP within cis- and trans-4 in CD3OD appear
as a multiplet in the range δ 3.07-4.18 (similar to the
corresponding data for the PPh3 system, Table S1). Some
isolated yellow crystals were well characterized as an
isomeric mixture by elemental analysis, NMR spectroscopy,
and MS data; the 31P{1H} NMR spectra of the crystals
dissolved in CD3OD and of the in situ solution reveal (as
for the PPh3 system) that the isomer ratio was unchanged
from 298 to 213 K.
homogeneous hydroformylation and hydrogenation condi-
tions, where such cleavage is critical in determining catalytic
activity.13 Of note, reaction of 1 with THP generates RhCl-
(THP)4 and no P-C bond cleavage is seen.1
Reports on cleavage of a P-C bond concurrent with
formation of a P-O bond are rare. A close analogue of our
system is seen in work from Pringle’s group,10b which
reported P-C bond cleavage at PtII and PdII centers during
studies on metal complex-catalyzed addition of PH3 to
formaldehyde to give THP: [M{P,P-(HOCH2)2POCH2P(CH2-
OH)2}2]Cl2 complexes were isolated as a cis/trans mixture
from reaction of cis-MCl2(THP)2 (M ) Pt, Pd) with excess
THP in methanol. Analogous to our Rh systems, a phos-
phine-phosphinite ligand has been formed, but in contrast
to the Rh species, the substituents at each P atom are
hydroxymethyl; the Pt and Pd complexes were well char-
acterized but not crystallographically. A complicated mul-
tistep mechanism was presented and involved initial forma-
tion of a binuclear metal alkoxide derived from deprotonation
of a coordinated P(CH2OH)3 and a final ring closure by
nucleophilic attack of a coordinated PCH2O- moiety at a
second (mutually cis) coordinated P atom; the proton was
incorporated into a phosphonium species, while in our work
the proton becomes a component of a hydrocarbon product.
A similar proton loss from the THP and ring closure by
nucleophilic attack at a cis-PRR2′ moiety is likely the
essential mechanism in our Rh systems; none of the
commonly proposed mechanisms for metal-catalyzed P-C
bond cleavage (oxidative insertion of a low-valent metal into
the aryl- and alkyl-phosphorus bonds, electrophilic sub-
stitution, and o-metalation processes)14,15 seems appropriate
for the Rh systems. A related example from Pregosin’s
group16 is P-C bond cleavage of a OTf-RuII-P(OH)Ph2
moiety induced by external MeOH to form a species
containing the Ph-RuII-P(OH)(OMe)Ph moiety with HOTf
as co-product; here the MeOH proton removes coordinated
triflate which is replaced by a Ph of the phosphine and the
methoxide replaces the phosphine phenyl. Less germane
examples of P-C bond cleavage within a coordinated PPh3
with co-formation of a P-O bond include that of an IrIII
system, the cleavage being induced by a carbonyl oxygen
of a coordinated dibenzoylmethylene moiety,17 and that of
a PdII system, where an acetate ligand provides the oxygen
source.18 We are unaware of any reports of cleavage of an
aryl-phosphine P-C bond induced by a -CH2OH func-
tionality, with co-formation of a hydrocarbon. More common
for coordinated THP is loss of formaldehyde with formation
2
2
The reactivity of 1 with PEtPh2, PMePh2, P(p-tol)3, P(p-
F-C6H4)3, and PnPr3 was qualitatively the same as that
described for the PPh3 and PCyPh2 systems: in situ reactions
revealed P-C bond cleavage with formation of cis- and
trans-RhCl(PRR′2)[P,P-R′(R)POCH2P(CH2OH)2] in a ratio
of ∼1, with concomitant generation of the hydrocarbon:
benzene for the first two systems and then, respectively,
1
toluene, fluorobenzene, and propane. The 31P{1H} and H
NMR data for the cis and trans isomer products, using the
labeling of Figure 2, are summarized in Tables S1 and S2.
Further evidence for an intermediate such as 2 (seen with
PPh3, Scheme 1) was seen only in the P(p-F-C6H4)3 system,
where cis-RhCl(P(p-F-C6H4)3)2(THP) was detected: δP
20.00 (ddd, Pa(THP), JPaRh ) 130.9, JPaPb ) 324.0, JPaPc
40.7), 33.78 (ddd, Pb(p-F-C6H4)3 trans to THP, JPbRh
)
)
142.9, JPbPa ) 324.0, JPbPc ) 38.0), and 49.06 (ddd, Pc(p-
F-C6H4)3 trans to Cl, JPcRh ) 192.5, JPcPa ) 40.7, JPcPb
)
38.0). The aryl-containing phosphine systems took ∼12 h
to generate the equilibrium isomer mixture, while the PnPr3
system was noticeably slower (>1 day); this is consistent
with more general facile, metal-catalyzed cleavage of P-aryl
bonds versus P-alkyl bonds, at least as substantiated under
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Lorenzini et al.
of PH(CH2OH)2, a reverse step in metal complex-catalyzed
synthesis of THP from PH3 and CH2O.10
Section. The correct version was posted on September 18,
2007.
Acknowledgment. We thank the Natural Sciences and
Engineering Research Council of Canada for financial
support via a Discovery Grant.
Supporting Information Available: General experimental
1
procedure, H and 31P{1H} NMR data (Tables S1, S2), and CIF
file for cis-4. This material is available free of charge via the Internet
at http://pubs.acs.org.
Note Added after ASAP Publication. This article was
released ASAP on September 15, 2007 with several incorrect
sub values to J in complexes 3 and 4 of the Experimental
IC7012182
9002 Inorganic Chemistry, Vol. 46, No. 21, 2007