Platinum complexes of a borane-Appended Analogue of 1,1'-Bis(diphenylphosphino)ferrocene: Flexible borane coordination modes and in situ vinylborane formation

Article abstract of DOI:10.1002/chem.201404846

A bis(phosphine)borane ambiphilic ligand, [Fe(h^5-C₅H₄PPh₂)(h^5-C₅H₄PtBu{C₆H₄ (BPh₂)-ortho})] (FcPPB), in which the borane occupies a terminal posi

Full text of DOI:10.1002/chem.201404846

DOI: 10.1002/chem.201404846
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Boranes |Very Important Paper|
Platinum Complexes of a Borane-Appended Analogue of 1,1’-
Bis(diphenylphosphino)ferrocene: Flexible Borane Coordination
Modes and in situ Vinylborane Formation
Bradley E. Cowie and David J. H. Emslie*[a]
Abstract: A bis(phosphine)borane ambiphilic ligand, [Fe(h5-
C5H4PPh2)(h5-C5H4PtBu{C6H4(BPh2)-ortho})] (FcPPB), in which the
borane occupies a terminal position, was prepared. Reaction
of FcPPB with tris(norbornene)platinum(0) provided [Pt(FcPPB)]
(1) in which the arylborane is h3BCC-coordinated. Subsequent
reaction with CO and CNXyl (Xyl=2,6-dimethylphenyl) afford-
ed [PtL(FcPPB)] {L=CO (2) and CNXyl (3)} featuring h2BC- and
h1B-arylborane coordination modes, respectively. Reaction of
1 or 2 with H2 yielded [PtH(m-H)(FcPPB)] in which the borane
is bound to a hydride ligand on platinum. Addition of PhC2H
to [Pt(FcPPB)] afforded [Pt(C2Ph)(m-H)(FcPPB)] (5), which rapidly
converted to [Pt(FcPPB’)] (6; FcPPB’=[Fe(h5-C5H4PPh2)(h5-
C5H4PtBu{C6H4(BPh-CPh=CHPh-Z)-ortho}]) in which the newly
formed vinylborane is h3BCC-coordinated. Unlike arylborane
complex 1, vinylborane complex 6 does not react with CO,
CNXyl, H2 or HC2Ph at room temperature.
Introduction
They are therefore of emerging interest as supporting
ligands in catalysis.[12,14–16] While h1B-coordinated complexes of
simple borane ligands have proven elusive, the use of ambi-
philic ligands, which contain both Lewis basic donors and
a Lewis acidic s-acceptors within the same ligand framework,
has provided access to a range of supported transitionmetal–
borane complexes. This concept was first demonstrated in
1999 when Hill et al. reported the reaction of Na[HB(mt)3] with
[RuCl(R)(CO)(PPh3)2] {R=CH=CHCPh2OH, CH=CH2, CH=CH(p-
MeC6H4) or Ph} to afford [Ru{B(mt)3}(CO)(PPh3)] (mt=2-sulfanyl-
1-methylimidazole); the borane in this complex was generated
in situ by RH elimination from initially formed [Ru(R)(CO)
(PPh3){HB(mt)3}].[17] Although effective, in situ ambiphilic ligand
generation lacks some generality, and has primarily been
observed for tris(pyrazolyl)hydroborate and related facially
capping hydroborate anions.
Monodentate s-donating ligands, with or without the possibili-
ty for p-donation or p-acceptance, are ubiquitous in transition-
metal chemistry, either as neutral donors (e.g. NH3, PR3, CO;
L-type ligands) or anionic donors (e.g., ClÀ, NR2À, HÀ; X-type li-
gands). By contrast, s-acceptor ligands (e.g., Group 13 Lewis
acids), designated Z-type ligands, are rare, and complexes
bearing s-acceptor ligands have the potential to promote
unique reactivity given their:
1) High trans influence.[1,2]
2) Ability to reduce the number of d-electrons in a complex
by two units (i.e., the number of electrons in the frontier
orbitals) without changing the overall electron count.
3) Propensity to yield compounds with unusual coordination
geometries.[3,4]
In
2006,
Bourissou
reported
the
synthesis
of
4) Ability to stabilise complexes in a range of oxidation states
by modulating the amount of electron density at the metal
centre through metal–Lewis acid interactions of varying
strength.[5,6]
[AuCl{(iPr2P)C6H4BR2] (BR2 =BCy2, BFlu; Flu=fluorenyl), which
features h1B-coordination; this complex was prepared by the
reaction of isolated (iPr2P)C6H4BR2 (BR2 =BCy2, BFlu) with [AuCl-
(SMe2)].[7] Related [o-(R2P)C6H4]2BPh (R=iPr, Ph) and [o-
(iPr2P)C6H4)]3B ligands were subsequently prepared, and de-
ployed in the preparation of Rh, Ni, Pd, Pt, Cu, Ag, and Au
complexes, all of which exhibit h1B-borane coordination to the
metal centre.[4,7,18] The chemistry of these ligands and closely
related derivatives has recently been expanded by
Peters,[1,6,12,14,15,19] Nakazawa,[20,21] Stephan,[22] Echavarren,[23] and
Bourissou.[16,24]
5) Potential to engage in Lewis acid–substrate or metal–co-
ligand–Lewis acid bridging interactions.[7,8]
6) Potential to form zwitterions through anionic ligand ab-
straction, in some cases resulting in substituent exchange
between boron and the metal centre.[9–12]
7) Potential to promote 1,1-insertion reactions.[13]
Also in 2006, we reported an isolable ambiphilic ligand,
TXPB (2,7-di-tert-butyl-5-diphenylboryl-4-diphenylphosphino-
9,9-dimethylthioxanthene), which features a phosphine donor
and a borane acceptor anchored to a rigid thioxanthene back-
bone. In contrast to the aforementioned phosphine–borane
ligands, TXPB did not yield h1B-borane complexes. Instead,
[a] B. E. Cowie, Prof. D. J. H. Emslie
Department of Chemistry and Chemical Biology
McMaster University, 1280 Main St. West
Hamilton, Ontario, L8S 4M1 (Canada)
E-mail: emslied@mcmaster.ca
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/chem.201404846.
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[Ni(TXPB)], [Pd(TXPB)] and [(TXPB)Rh(m-CO)2Fe(CO)Cp] were iso-
lated featuring h3BCC-arylborane coordination through boron
and the ipso- and ortho-carbon atoms of a B-phenyl ring.[25,26]
Additionally, an h2BC-arylborane complex, [Rh(CO)(TXPB)][PF6],
was isolated, in which rhodium is coordinated to boron and
the ipso-carbon of a B-phenyl ring.[11]
tive to TXPB, while a rigid phenylene linker between the cen-
tral donor and the borane is maintained in both TXPB and
FcPPB. The borane in FcPPB is positioned at the extremity of
the ligand framework, as is the case in TXPB; this is potentially
desirable as a means to encourage the pendant borane to in-
teract with substrates and co-ligands, with a view towards ac-
cessing cooperative reactivity involving both the metal and
the borane. The FcPPB ligand can be considered a more elec-
tron-donating and borane-substituted analogue of dppf [1,1’-
bis(diphenylphosphino)ferrocene]; a wide bite-angle bisphos-
phine ligand used extensively in late-transition-metal cataly-
sis.[29] A range of FcPPB platinum complexes are described
herein, each one featuring a different FcPPB coordination
mode. Furthermore, the reaction of phenylacetylene with plati-
num-coordinated FcPPB is described, transforming the arylbor-
ane (R2B-Ph) group in FcPPB to a vinylborane (R2B-CPh=CHPh).
The pendant borane in TXPB also proved to be available to
participate in bonding with a range of co-ligands. For example,
addition of TXPB to [Pd2(dba)3] (dba=trans,trans-dibenzylide-
neacetone) afforded [Pd(dba)(TXPB)], in which dba bridges be-
tween palladium and boron to generate a zwitterionic h3-bora-
toxyallyl complex.[10] Furthermore, addition of isonitriles (RNC;
R=nBu, 2,6-dimethylphenyl, para-chlorophenyl) to [(TXPB)
Rh(m-CO)2Fe(CO)Cp] provided [(TXPB)Rh(m-CNR)(m-CO)Fe(CO)
Cp] complexes that feature a bridging borataaminocarbyne
ligand.[27] Additionally, a range of Rh, Pd, and Pt complexes
with a halide bridging between the metal and the borane
have been isolated.[11,28]
Results and Discussion
Although the TXPB ligand has been used to prepare a broad
range of complexes, the central thioether donor is undesirably
susceptible to displacement from the metal centre, especially
in low-valent complexes. For example, addition of dvds
(dvds=1,3-divinyltetramethydisiloxane) to [Pd(TXPB)] formed
[Pd(h2:h2-dvds)(k1P-TXPB)], in which Pd is removed from the
central binding pocket of the ligand and TXPB acts as a mono-
dentate phosphine.[26] Furthermore, addition of CO to
[Pd(TXPB)] resulted in complete displacement of the TXPB
ligand from the metal.
The new PPB-donor/acceptor ligand, 1’-{(ortho-diphenylboryl-
phenyl)-tert-butylphosphino}-1-diphenylphosphinoferrocene
(FcPPB), was accessed in seven steps, as shown in Scheme 1.
Known [Fe(h5-C5H4Br)(h5-C5H4PPh2)] was prepared as previously
reported,[30] and the 2-bromophenyl-tert-butylphosphine
moiety was incorporated into the ligand backbone by lithiation
of the remaining bromide followed by quenching with (o-
BrC6H4)tBuPCl; (o-BrC6H4)tBuPCl was prepared in three steps
from commercially available 1,2-dibromobenzene and
ClP(NEt2)2. Finally, lithiation of [Fe(h5-C5H4PPh2){h5-C5H4PtBu
(C6H4Br-o)}] followed by the addition of BrBPh2 provided FcPPB.
Intermediates (o-BrC6H4)tBuPCl and [Fe(h5-C5H4Br)(h5-C5H4PPh2)]
were prepared on a 5–10 gram scale, and each of the final two
steps proceeded in 70–80% yield, making FcPPB accessible in
multi-gram quantities. FcPPB is chiral at phosphorus, and was
used as a mixture of enantiomers.
Herein we describe the syntheis of a new borane-containing
ambiphilic ligand, FcPPB ([Fe(h5-C5H4PPh2)(h5-C5H4PtBu{C6H4
(BPh2)-ortho})]; Scheme 1). This ligand features a bisphosphine
donor set in place of the phosphine–thioether donor set of
TXPB, thus improving the overall donor ability of the ligand.
The ferrocene unit located between the two phosphorus
donors in FcPPB provides increased coordinative flexibility rela-
X-ray quality crystals of FcPPB were grown by slow evapora-
tion of a solution in CH2Cl2/hexanes at 298 K. The solid-state
structure of FcPPB (Figure 1) revealed adduct formation be-
tween the tert-butyl-substituted phosphorus donor, P(2), and
the borane; the BÀP(2) bond length in FcPPB is 2.146(2) ꢁ, the
P(2)-C(27)-C(28) and B-C(28)-C(27) angles are 98.4(1)8 and
106.6(1)8, respectively (rather than 1208) and the sum of the C-
B-C angles is 347.5(2)8 (rather than 3608). The BÀP(2) bond
length in FcPPB is very similar to the BÀP distance in [o-
(iPr2P)C6H4]3B (BÀP=2.150(3) ꢁ).[31] The 11B NMR signal for
FcPPB in [D6]benzene is 17 ppm, which is at a much lower fre-
quency than expected for a free triarylborane, indicating that
phosphine–borane adduct formation persists in solution.[32]
shift in the 31P NMR signal for the C5H4P(tBu)Ar moiety from
4.9 ppm in to
[Fe(h5-C5H4PPh2){h5-C5H4PtBu(C6H4Br-o)}]
19.7 ppm in FcPPB further supports this interpretation.
A
Reaction of FcPPB with [Pt(nb)3] (nb=norbornene) yielded
a pale yellow solid identified as [Pt(FcPPB)] (1) by multinuclear
NMR spectroscopy, combustion elemental analysis, and X-ray
crystallography. The 11B NMR chemical shift of 21 ppm is indica-
tive of four-coordinate boron, and although the B-phenyl
1
Scheme 1. Synthesis of FcPPB.
groups give rise to just three signals in the H NMR spectrum
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2.0751(8) and 2.1616(8) ꢁ, respectively in [Ni(PhDPBMes)]
[PhDPBMes =MesB{(o-Ph2P)C6H4}2; Mes=2,4,6-trimethylphenyl].[14]
Although the MÀB, MÀCortho and MÀCipso distances in 1 and [Pd-
(TXPB)] are equal within error, the 11B NMR chemical shift for
1 is significantly lower in frequency than those for [Pd(TXPB)]
and [Ni(TXPB)] (20 versus 31 and 30 ppm, respectively), consis-
tent with 1) increased electron donation from the metal to the
borane in 1, due to the increased donor ability of the central
phosphine donor of FcPPB relative to the thioether group in
TXPB,[26] and 2) the increased basicity of Pt relative to Pd and
Ni.[18a]
Reaction of 1 with CO or CNXyl (Xyl=2,6-dimethylphenyl)
afforded [Pt(CO)(FcPPB)] (2) and [Pt(CNXyl)(FcPPB)] (3)
(Scheme 2) with n(CO) and n(CN) of 1982 and 2128 cmÀ1 in
Figure 1. Solid-state structure of FcPPB with ellipsoids drawn at 50% proba-
bility. Hydrogen atoms have been omitted for clarity. Selected bond lengths
[ꢁ] and angles [8]: P(2)ÀB(1), 2.146(2); C(28)-B(1)-C(33), 115.2(2); C(28)-B(1)-
C(39), 118.2(1); C(33)-B(1)-C(39), 114.1(1); C(28)-B(1)-P(2), 79.1(1); C(27)-P(2)-
B(1), 75.73(8).
at 25 and À908C, single-crystal X-ray diffraction revealed
h3BCC-arylborane coordination to platinum in the solid-state
(Figure 2), with PtÀB, PtÀCipso and PtÀCortho distances of
2.292(3), 2.225(3) and 2.329(3) ꢁ, respectively. Boron is only
slightly pyramidalised with the sum of the C-B-C angles equal
to 354.3(5)8, and the geometry at platinum is pseudo square
planar, analogous to that in [Pt(h3-allyl)(PPh3)2]+.[33] The MÀB,
MÀCipso and MÀCortho bond lengths in previously reported h3-ar-
ylborane complexes of Group 10 metals are 2.320(5), 2.198(4)
and 2.325(4) ꢁ, respectively, in [Pd(TXPB)], 2.297(4) ꢁ, 2.019(3)
and 2.081(3) ꢁ, respectively, in [Ni(TXPB)],[26] and 2.1543(9),
Scheme 2. Synthesis of [Pt(FcPPB)] (1), [Pt(CO)(FcPPB)] (2), [Pt(CNXyl)(FcPPB)]
(3) and [PtH(m-H)(FcPPB)] (4).
CH2Cl2, respectively, consistent with terminally bound carbonyl
and isonitrile ligands.[34] Compound 2 did not react with
B(C6F5)3, whereas compound 3 reacted over days when heated
to 908C to re-form complex 1. For 2 and 3, as in complex 1,
each of the B-phenyl groups gave rise to just three signals in
1
the H NMR spectrum between 25 and À908C. The 11B chemi-
cal shifts for 2 and 3 are 19 and 10 ppm, consistent with four-
coordinate boron.
Single crystals of 2 were obtained from CH2Cl2/hexane at
À308C, and X-ray diffraction revealed that the h3BCC-arylbor-
ane coordination mode in 1 has been converted to an h2BC-co-
ordination mode in 2 (Figure 3). The two phosphorus donors,
CO and Cipso (CO=C(45); Cipso =C(33)) adopt a distorted tetra-
hedral arrangement around platinum with a 73.28 angle be-
tween the P(1)-Pt-P(2) plane and the C(33)-Pt-C(45) plane (the
angle between the the P(1)-Pt-P(2) plane and the B-Pt-C(45)
plane is 50.48). The P(1)-Pt-P(2), P(X)-Pt-C(45) (X=1 or 2), P(2)-
Pt-C(33) and C(33)-Pt-C(45) angles are all between 100 and
Figure 2. Solid-state structure of 1·CH2Cl2 with ellipsoids drawn at 50% prob-
ability. Hydrogen atoms and lattice solvent have been omitted for clarity.
Selected bond lengths [ꢁ] and angles [8] for 1·CH2Cl2: Pt(1)ÀB(1), 2.292(3);
Pt(1)ÀC(33), 2.225(3); Pt(1)ÀC(34), 2.329(3); Pt(1)ÀP(1), 2.3014(8); Pt(1)ÀP(2),
2.2342(9); B(1)ÀC(33), 1.551(5); C(28)-B(1)-C(33), 118.4(3); C(28)-B(1)-C(39),
117.6(3); C(33)-B(1)-C(39), 118.0(3); P(1)-Pt(1)-B(1), 171.1(1); P(2)-Pt(1)-C(34),
148.32(7).
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Figure 3. Solid-state structure of 2·2CH2Cl2 with ellipsoids drawn at 50%
probability. Hydrogen atoms and lattice solvent have been omitted for clari-
ty. Selected bond lengths [ꢁ] and angles [8] for 2·2CH2Cl2: Pt(1)ÀB(1),
2.319(5); Pt(1)ÀC(33), 2.490(5); Pt(1)ÀP(1), 2.369(1); Pt(1)ÀP(2), 2.284(1); B(1)À
C(33), 1.597(7); C(28)-B(1)-C(33), 114.9(4); C(28)-B(1)-C(39), 113.4(4); C(33)-
B(1)-C(39), 116.7(4); P(2)-Pt(1)-B(1), 82.4(1); P(1)-Pt(1)-B(1), 146.2(1); B(1)-Pt(1)-
C(45), 88.9(2).
Figure 4. Solid-state structure of 3·CH2Cl2 (only one of the two independent
molecules in the unit cell is shown) with ellipsoids drawn at 50% probability.
Hydrogen atoms and lattice solvent have been omitted for clarity. Selected
bond lengths [ꢁ] and angles [8] for 3·CH2Cl2: Pt(1A)ÀB(1A), 2.273(12); Pt(1A)À
C(45A), 1.952(10); Pt(1A)ÀP(1A), 2.381(2); Pt(1A)ÀP(2A), 2.268(3); C(45A)À
N(1A), 1.170(12); C(28A)-B(1A)-C(33A), 109.1(8); C(28A)-B(1A)-C(39A),
109.9(8); C(33A)-B(1A)-C(39A), 114.0(8); C(45A)-N(1A)-C(46A), 176.2(9);
Pt(1B)ÀB(1B), 2.281(11); Pt(1B)ÀC(45B), 1.978(9); Pt(1B)ÀP(1B), 2.369(2);
Pt(1B)ÀP(2B), 2.271(2); C(45B)ÀN(1B), 1.147(11); C(28B)-B(1B)-C(33B), 108.4(8);
C(28B)-B(1B)-C(39B), 111.5(8); C(33B)-B(1B)-C(39B), 113.4(8); C(45B)-N(1B)-
C(46B), 175.1(9).
1078, whereas P(2)-Pt-C(45) is 134.0(2)8. The PtÀB and PtÀCipso
distances are 2.319(5) and 2.490(5) ꢁ, respectively, and boron is
significantly pyramidalised with the sum of the C-B-C angles
equal to 345.0(7)8. Related Group 10 complexes featuring bi-
sphosphine and h2BC-arylborane coordination include [Ni(thf)
(PhDPBPh)] (RDPBPh =PhB{(o-R2P)C6H4}2; NiÀB: 2.124(2) ꢁ; NiÀCipso
:
2.176(2) ꢁ; S(C-B-C): 352.1(3)8),[14] and [Ni(N2)(iPrDPBPh)] (NiÀB:
2.201(2)/2.181(2) ꢁ; NiÀCipso: 2.170(2)/2.149(2) ꢁ; S(C-B-C): 3538;
11B NMR 20 ppm).[1] Similarly to 2, the two phosphorus donors,
Cipso and the remaining co-ligand (THF and N2, respectively), in
the above nickel complexes exhibit distorted tetrahedral ge-
ometry. While the MÀB bond lengths in the above two litera-
ture complexes are in good agreement with 2, taking into ac-
count the smaller covalent radius of Ni (1.24 ꢁ) versus Pt
(1.36 ꢁ),[35] the MÀCipso bond length in 2 is significantly longer
than those in the nickel complexes and boron is more pyrami-
dal, indicating that the arylborane–platinum coordination in 2
consists of a strong PtÀB and a weak PtÀCipso bonding interac-
tion. The PtÀCipso distance in 2 is also significantly longer than
either the PtÀCipso or the PtÀCortho distance in 1, despite compa-
rable PtÀB bond lengths.
ferent P(1)-Cent1–5-Cent6–10-P(2) (Centx–y =centroid of the cyclo-
pentadienyl ring containing atoms C(x) to C(y)) dihedral
angles: À30.4, À20.9 and 4.4/À0.98 in 1, 2 and 3, respectively.
The 195Pt resonances for 1–3 are located at À4934, À4422
and À4486 ppm, respectively. In the 31P{1H} NMR spectra of 1–
3, the C5H4PPh2 signal is observed at 28.5, 22.8 and 21.8 ppm,
respectively (1J(31P-195Pt)=4183, 2343 and 1381 Hz), and the
C5H4P(tBu)Ar group is observed at 50.8, 59.4 and 62.7 ppm, re-
spectively (1J(31P-195Pt)=5651, 4884 and 4549 Hz). The marked
decrease in 31P-195Pt coupling constants for the C5H4PPh2
groups in 1–3 is likely due to the changes in arylborane coordi-
nation mode, with a greater trans-influence exerted by the h1-
borane, even though the P(1)-Pt-B bond angle more closely
approaches 1808 in compound 1 (P(1)-Pt-B=171.0(1)8 in 1,
146.2(1)8 in 2, and 157.9(3)–159.9(3)8 in 3). A marked increase
in peak broadness is also observed in the 195Pt{1H} NMR spectra
for 1–3, with w1/2 increasing from 95 to 125 to 300 Hz,
respectively, arguably due to stronger bonding of platinum to
quadrupolar boron in the order 1<2<3.
X-ray quality crystals of complex 3 were grown by slow dif-
fusion of hexanes into a solution of 3 in CH2Cl2 at À308C; 3
crystallises with two independent molecules within the unit
cell. In contrast to 1 and 2, the borane in compound 3 is h1B-
coordinated, and the geometry at platinum is distorted square
planar with P(1)-Pt-B and P(2)-Pt-C(45) angles of 157.9(3) and
159.9(3)8, respectively (Figure 4). The PtÀB distance is 2.27(1)/
2.28(1) ꢁ and boron is almost tetrahedral with the sum of the
C-B-C angles equal to 333(1)8. The P(1)-Pt-P(2) bite angle de-
creases from 108.53(3)8 in 1, to 104.56(4)8 in 2, and 100.7(1)/
101.0(1)8 in 3, and the conformational flexibility of the bi-
s(phosphino)ferrocene backbone is highlighted by the very dif-
Reaction of 1 with H2 (1 atm) afforded [PtH(m-H)(FcPPB)] (4),
which is also generated by exposing carbonyl complex 3 to H2
(1 atm). Compound 4 is stable under an atmosphere of H2, but
in solution under argon (slowly) or under vacuum (rapidly) it
loses H2 to re-form 1 (Scheme 2). Additionally, under an atmos-
phere of CO, 4 readily re-forms carbonyl complex 2. The hy-
dride signals for 4 are located at À2.76 and À5.19 ppm in the
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1H NMR spectrum. The lower frequency hydride signal is
a sharp doublet-of-doublets and is trans to the C5H4P(tBu)Ar
group, whereas the hydride ligand trans to the C5H4PPh2 group
is a slightly broadened doublet-of-doublets, suggestive of a Pt-
H-B bridging interaction; the 11B NMR chemical shift of 5 ppm
is consistent with this assignment.
Solid-state IR spectroscopy of 4 was not possible due to the
propensity of 4 to eliminate H2 in the absence of a hydrogen
atmosphere. However, in CH2Cl2 broad PtÀH and very broad
PtÀHÀB stretches were located at 2020 and 1822 cmÀ1, respec-
tively, in fair agreement with calculated values (2065 and
1868 cmÀ1; see the Experimental Section for details of the calu-
lations). The PtÀH stretch for the terminally bound hydride is
also in good agreement with platinum complexes
cis-[PtH(SetBu)(PPh3)2] (n(PtÀH)=2088 cmÀ1)[36] and [Pt2H2(m-
PR2)2(PEt3)2] (n(PtÀH)=2004 cmÀ1 (R=Ph); 2022 cmÀ1 (R=
tBu))[37] Furthermore, [PtD(m-D)(FcPPB)] ([D]-4) was prepared
from the reaction of [Pt(FcPPB)] with D2, and the PtÀD stretch-
ing frequency (1478 cmÀ1) was located by subtraction of the IR
spectrum of 4 from that of [D]-4 due to overlap of these
stretches with the C=C and CÀC stretches (the Pt-D-B stretch
was not located).
Figure 5. Calculated structure of 4 with most hydrogen atoms omitted for
clarity.
92.4, with the acute angle to the phenyl ipso-carbon, C(33),
which is closest to trans to platinum across the HÀB bond {Pt-
H-B-C(33) torsion angle=1538}; an acute (<1008) H-B-C angle
was previously observed in the experimental and calculated
structures of [Rh(m-H)(PPh3)(CO)n{PhB(C6H4PPh2-ortho)2}] (n=0
and 1).[21]
Complete abstraction of the hydride ligand from platinum
by boron does not occur in 4, given that both hydride signals
1
show coupling to 31P and 195Pt. However, a smaller H-195Pt cou-
The potential of 1 to hydrogenate alkenes and internal al-
kynes (C2H4, styrene, norbornene, cyclooctene, 1-octene, C2Ph2;
20 or 608C) was investigated, but significant catalytic activity
was only observed for certain batches, and only in the absence
of metallic mercury, indicative of heterogeneous catalysis by
a small amount of elemental platinum. This contrasts the hy-
drogenation activity of the first row ambiphilic ligand com-
plexes [Fe(N2)(iPrTPB)] and [Ni(iPrDPBMes)] (iPrTPB=B{(o-
iPr2P)C6H4}3; iPrDPBMes =MesB{(o-iPr2P)C6H4}2) reported recently
by Peters et al.[12,14] Compound 1 does not react with any of
the aforementioned alkenes or alkynes to an extent detectable
pling is observed for the bridging hydride (792 vs. 905 Hz),
consistent with a weakened PtÀH bond, despite its position
trans to the lower trans-influence phosphine. The greater
trans-influence of the terminal hydride is also evident from the
1
31P{1H} NMR spectrum of 4, which shows a larger J(31P-195Pt)
coupling of 3721 Hz for the C5H4PPh2 group (trans to the
bridging hydride), relative to 2123 Hz for the C5H4P(tBu)Ar
group, even though the latter is the better donor and has the
1
higher J(31P-195Pt) coupling in complexes 1–3. The 195Pt signal
for 4 is a sharp doublet-of-doublets located at À4980 ppm.
Due to the propensity for 4 to revert back to 1 and H2 in the
absence of an H2 atmosphere, we were unsuccessful in obtain-
ing single crystals of 4. However, DFT calculations on 4 (see
the Experimental Section for details of the calulations) con-
verged to a minimum with one bridging and one terminal hy-
dride (Figure 5), consistent with the NMR data. The geometry
at platinum is square planar, with PtÀP distances of 2.246 and
2.322 ꢁ to the C5H4PPh2 and C5H4P(tBu)Ar groups, respectively
(the corresponding Mayer bond orders are 1.21 and 1.05), and
PtÀH distances of 1.613 and 1.686 ꢁ to the terminal and bridg-
ing hydride ligands, respectively. Boron is significantly pyrami-
dalised [S(C-B-C): 3388], the PtÀB distance remains fairly short
at 2.524 ꢁ, and the BÀH distance is 1.386 ꢁ, which is longer
than that observed for a free hydroborate anion (e.g., 1.10(2) ꢁ
in [HC(SiMe2OCH2CH2OCH3)3Na][Ph3BH]).[38] The Hirshfeld charg-
es on Pt and B are 0.106 and À0.015, and the charges on the
terminal and bridging hydrogen atoms are À0.093 and
À0.048, indicating that 4 is not well represented as a zwitterion.
The PtÀH(terminal), PtÀH(bridging), HÀB and PtÀB Mayer bond
orders are 0.81, 0.58, 0.39 and 0.23, respectively, suggesting
that the borane in 4 interacts with both the bridging hydride
and the metal centre. The H-B-C angles are 115.4, 109.3 and
1
by H NMR spectroscopy. By contrast, reaction of 1 with PhC2H
resulted in rapid oxidative addition to provide [Pt(C2Ph)(m-
H)(FcPPB)] (5), which isomerised within minutes to afford an
h3BCC-coordinated vinylborane complex, [Pt(FcPPB’)] (6A;
FcPPB’=[Fe(h5-C5H4PPh2)(h5-C5H4PtBu{C6H4(BPh-CPh=CHPh-Z)-
ortho}]); after 5 minutes at room temperature, the reaction of
1 with PhC2H contained a 1:1 mixture of 5 and 6A. (Scheme 3).
The hydride signal in 5 is located at À3.69 ppm in the
1
1H NMR spectrum, with a J(1H-195Pt) coupling of 760 Hz and
2J(1H-31P) couplings of 115 and 12 Hz. An 11B NMR chemical
shift of 11 ppm indicates that the hydride ligand in 5 resides in
a bridging position between platinum and boron, as was ob-
served in 4. The CꢀC stretch for 5 was located at 2126 cmÀ1 in
the IR spectrum,[39] which is very similar to that observed for
trans-[PtH(C2C6H4Me-p)(PPh3)2] (n(CꢀC)=2111 cmÀ1).[40] Similar
oxidative addition reactivity with HC2Ph was reported recently
for [Fe(N2)(iPrTPB)], but in this case the resulting hydride is com-
pletely abstracted by the borane to afford zwitterionic [Fe
(C2Ph)(iPrTPB-H)] (n(CꢀC)=2040 cmÀ1; n(BÀH)=2490 cmÀ1).[12]
Complex 6A is a vinylborane analogue of arylborane com-
plex 1, and both complexes feature an h3BCC-coordination
mode, almost identical 31P NMR chemical shifts (50.3 and 27.6
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Figure 6. Solid-state structure of 6A·4C6H6 with ellipsoids drawn at 50%
probability. With the exception of H(46), all hydrogen atoms and lattice sol-
vent have been omitted for clarity. Selected bond lengths [ꢁ] and angles [8]
for 6A·4C6H6: Pt(1)ÀB(1), 2.303(6); Pt(1)ÀC(45), 2.184(5); Pt(1)ÀC(46),
2.194(5); Pt(1)ÀP(1), 2.295(2); Pt(1)ÀP(2), 2.278(1); B(1)ÀC(45), 1.546(8);
C(45)ÀC(46), 1.447(8); C(28)-B(1)-C(45), 115.1(5); C(28)-B(1)-C(39), 117.4(5);
C(39)-B(1)-C(45), 124.0(5); C(45)-C(46)-C(47), 123.2(5); C(33)-C(45)-C(46),
118.4(5); C(33)-C(45)-B(1), 121.5(5); C(45)-C(46)-H(46), 123(4); C(47)-C(46)-
H(46), 109(4).
Scheme 3. Synthesis of [Pt(C2Ph)(m-H)(FcPPB)] (5) and [Pt(FcPPB’)](6A/6B).
for 6A, 50.8 and 28.5 ppm for 1) and similar 11B NMR chemical
shifts (24 and 21 ppm for 6A and 1, respectively). The plati-
num resonance is a sharp doublet-of-doublets located at
À5117 ppm in the 195Pt{1H} NMR spectrum. In the 1H NMR spec-
trum of 6A, the BCPh=CHPh signal is observed at 5.86 ppm as
a doublet-of-doublets with platinum satelites. The vinyl carbon
atoms in 6A are located at 114.0 (Ca, broad singlet) and
77.7 ppm (Cb, dd, 2J(13C-31P)=34, 4 Hz) in the 13C NMR spec-
trum, demonstrating that h3BCC-vinylborane coordination is
maintained in solution, in contrast to h3BCC-arylborane coordi-
unfortunately, the standard deviation associated with the BÀCa
bond in 6A is too large to draw any conclusions regarding the
extent of multiple bond character. The vinylic proton and the
BÀPh ring (H(46) and C(39)) reside in the exo-positions of the
coordinated vinyl group and are located 0.419 and 0.922 ꢁ
above the B-Ca-Cb plane, respectively, whereas CbÀPh and the
phenylene linker of the backbone (C(47) and C(28)) reside in
endo-positions and bend towards the metal, placing them
0.565 and 0.086 ꢁ below the B-Ca-Cb plane, respectively. Such
distortions are typical of late transition metal–allyl
complexes,[42] suggesting that the vinylborane in 6A is more
borataallyl-like than alkyl/borataalkene-like.[41]
1
nation in 1. The J(31P-195Pt) couplings for the C5H4PPh2 groups
in 6A and 1 are similar (3937 Hz in 6A vs 4183 Hz in 1), where-
1
as the J(31P-195Pt) coupling for the C5H4P(tBu)Ar group is much
smaller in 6A than that in 1 (3695 Hz in 6A vs 5651 Hz in 1),
suggesting that the vinyl group in 6A exerts a substantially
greater trans-influence than the phenyl group in 1. The im-
proved coordination ability of the B-vinyl group in 6A relative
to the B-phenyl group in 1 is also reflected in the reactivity of
6A, which does not react at room temperature with CO,
CNXyl, H2 or HC2Ph.
Complex 6A isomerises over a period of six days at room
temperature to an approximate 45:55 mixture of the original
isomer and a new isomer, 6B, giving rise to a new set of 31P
(55.7 and 23.3 ppm), 11B (30 ppm) and 195Pt (À4840 ppm) sig-
nals. As with 6A, isomer 6B features an h3BCC-coordinated (Z)-
(BÀCPh=CHPh) group: 1) 1H-13C HSQC NMR confirmed that the
vinyl proton is located in the b-position, 2) coupling between
the BÀCPh=CHPh signal and the o-BPh signal in a selective 1D
1H-1H ROESY NMR experiment demonstrated that the ligand
has a Z-arrangement of the phenyl substituents on the vinyl
group (the vinyl CH proton in 6A shows an analogous ROESY
coupling), 3) the 11B NMR chemical shift (30 ppm) confirmed
Single crystals of 6A were obtained from a benzene/hexane
solution cooled to À308C. In the solid-state, complex 6A
adopts a distorted square planar geometry, with P(2)-Pt-C(46)
and P(1)-Pt-B angles equal to 149.0(2) and 165.8(2)8, respec-
tively (Figure 6). The PtÀB distance is 2.303(6) ꢁ and the sum
of the C-B-C angles is 356.5(9)8; these data are identical within
error to those in 1. By contrast, the PtÀCa and PtÀCb distances
in 6A (2.184(5) and 2.194(5) ꢁ, respectively) are shorter than
those in 1 by 0.041 and 0.135 ꢁ. Even shorter PtÀC distances
have previously been described for [Pt(PtBu3)(VBPh)] [VBPh =(E)-
PhHC=C(H)-B(C6F5)2; two independent molecules in the unit
cell; PtÀCa =2.126(4)/2.130(4) ꢁ; PtÀCb =2.137(4)/2.155(4) ꢁ;
PtÀB=2.273(5)/2.319(5) ꢁ],[41] likely due to decreased steric
hindrance and the greater Lewis acidity of the borane in VBPh
(VBPh was shown to be an overall acceptor ligand in [Pt(PtBu3)-
(VBPh)]). The BÀCa distance in 6A is 1.546(8) ꢁ, compared with
1.551(5) ꢁ in 1 and 1.517(6)/1.519(7) ꢁ in [Pt(PtBu3)(VBPh)], but
1
coordination of boron to platinum, and 4) vinyl group H-195Pt,
13C-195Pt and 13C-31P coupling confirmed coordination of both
the a- and b-carbon atoms of the vinyl ligand. The selective
1
1D H-1H ROESY NMR experiments also revealed that the vinyl
proton and the B-phenyl groups in both 6A and 6B are posi-
tioned in the exo positions of the h3BCC-coordinated vinylbor-
ane. Isomer 6B is therefore related to 6A by coordination of
platinum to the opposite face of the vinylborane, with all of
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the regiochemistry of the BCC unit preserved (Scheme 3;
isomer 6B shows through-space coupling between the
BÀCPh=CHPh group and the PCMe3 group).
Pathway A seems less likely given that [PtH(m-H)(FcPPB)]
does not eliminate benzene, which would be anticipated if the
pendant borane is able to abstract a hydride and return
a phenyl group to the metal centre. Additionally: 1) in the
presence of a large excess of HC2Ph, products consistent with
C2Ph2 substitution by HC2Ph and subsequent 1,2-insertion and
reductive elimination are not observed, and 2) if free rotation
or dissociation of C2Ph2 can occur, the phenyl group originat-
ing from boron could occupy either the a- or the b-position,
and only the former is observed when the reaction is conduct-
ed with HC2(C6D5). However, with respect to the 1,1-insertion
step in pathway B, it is of note that equivalent reactivity is not
observed for [Pt(CO)(FcPPB)] (2) or [Pt(CNXyl)(FcPPB)] (3),
which are analogues of proposed [Pt(=C=CHPh)(FcPPB)].
Two plausible reaction pathways for the formation of 6A
from 5 are shown in Scheme 4. Pathway A involves initial phe-
nylacetylene CÀH bond oxidative addition, exchange of a hy-
Conclusion
A wide bite-angle phosphine–phosphine–borane ambiphilic
ligand, FcPPB {[Fe(h5-C5H4PPh2)(h5-C5H4PtBu{C6H4(BPh2)-ortho})];
Scheme 1}, has been prepared and utilised in the synthesis of
a range of platinum complexes. This ligand is a borane-ap-
pended analogue of dppf {1,1’-bis(diphenylphosphino)ferro-
cene}, which is one of the most commonly employed bisphos-
phine ligands in late transition metal catalysis. FcPPB is a supe-
rior ligand framework relative to our formerly employed phos-
phine–thioether–borane ambiphilic ligand, TXPB, given its
overall improved donor ability and increased ligand backbone
flexibility. The reactivity of [Pt(FcPPB)] with CO, CNXyl, H2 and
HC2Ph highlights the coordinative flexibility of the triarylborane
unit in FcPPB, providing reversible access to h3BCC-, h2BC- and
h1B-borane coordination modes, as well as Pt-H-BR3 bridging
interactions. This reactivity also demonstrates the ability of the
FcPPB to promote oxidative addition, to maintain coordination
of both donor groups in a range of oxidation states and to sta-
bilise varied coordination geometries at platinum, ranging
from pseudo-square-planar to pseudo-tetrahedral. Further-
more, the reaction of [Pt(FcPPB)] with HC2Ph afforded
[Pt(FcPPB’)] (FcPPB’=[Fe(h5-C5H4PPh2)(h5-C5H4PtBu-{C6H4(BPh-
CPh=CHPh-Z)-ortho}]) featuring the first vinylborane-contain-
ing ambiphilic ligand. This complex provides a unique oppor-
tunity for direct comparison of h3BCC-arylborane and h3BCC-
vinylborane bonding and reactivity, and in the solid state
[Pt(FcPPB)] and [Pt(FcPPB’)] are structurally similar. However,
the latter features shorter PtÀC bonds, and whereas [Pt(FcPPB)]
reacts with CO, CNXyl, H2 and HC2Ph at room temperature,
[Pt(FcPPB’)] does not, consistent with much tighter h3BCC-coor-
dination in the vinylborane complex. This suggests that aryl-
borane-appended complexes are likely to be of more utility
than vinylborane-appended complexes in the future develop-
ment of cooperative catalysis. Overall, the application of ambi-
philic-ligand/transition-metal complexes for small molecule ac-
tivation and catalysis is a rapidly emerging field, and the re-
sults described herein demonstrate initial reactivity of a new
ambiphilic ligand featuring 1) a bisphosphine unit that is well
established in catalysis, and 2) a Lewis acid that occupies a ter-
minal position in a donor–donor–acceptor array (as opposed
to a central position in a donor–acceptor–donor array), poten-
Scheme 4. Two possible reaction pathways for the formation of 6A. Ph* in-
dicates the phenyl group originating from phenylacetylene. Only one possi-
ble geometry and/or borane coordination mode is shown for proposed in-
termediates. Pathways relying on BÀC bond-forming insertion reactions are
shown in grey. Reactions: (i) hydride abstraction by the borane, followed by
phenyl group transfer from boron to platinum, (ii) reductive elimination,
(iii) alkynyl hydride-alkyne-vinylidene isomerisation, (iv) oxidative addition,
(v) 1,2-insertion, (vi) 1,1-insertion.
dride on platinum with a phenyl group on boron, and CÀC
bond-forming reductive elimination to generate a platinum(0)
diphenylacetylene intermediate. Subsequent BÀH bond oxida-
tive addition, 1,2-insertion involving the C2Ph2 ligand and the
newly formed hydride ligand (or less likely the boryl ligand),
and reductive elimination yields 6A. By contrast, pathway B in-
volves initial vinylidene formation, followed by sequential BÀC
bond oxidative addition, 1,1-insertion involving the vinylidene
and a platinum phenyl or boryl group, and reductive elimina-
tion to form 6A. A pathway involving migration of the vinyli-
dene in [Pt(=C=CHPh)(FcPPB)] to a bridging position between
boron and platinum was not considered viable given the
electrophilic nature of the a-carbon of a vinylidene ligand.
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a Thermo EA1112 CHNS/O analyser. High-resolution (HR) electron
ionisation (EI) mass spectrometry measurements were carried out
on the Waters Micromass GCT instrument (quadrupole time-of-
flight). A VWR Clinical 200 large capacity centrifuge (with 288 fixed-
angle rotors that hold 12ꢂ15 mL or 6ꢂ50 mL tubes) in combina-
tion with VWR high-performance polypropylene conical centrifuge
tubes was used when required (inside the glovebox). NMR spec-
troscopy (1H, 13C{1H}, 11B, 31P{1H}, 195Pt{1H}, DEPT-135, uDEFT, COSY,
tially rendering it more accessible for substrate and co-ligand
coordination. Future work will explore the utility of FcPPB in
cooperative catalysis, and will compare the reactivity of FcPPB
with analogues bearing alternative Lewis acidic groups; prepa-
ration of the required ligands is expected to be straightforward
given that the Lewis acid is installed in the final step of the
FcPPB ligand synthesis.
ROESY, H,13C-HSQC, H,13C-HMBC, H,31P-HMBC) was performed on
Bruker DRX-500 and AV-600 spectrometers. All 1H NMR and
13C NMR spectra were referenced relative to SiMe4 through a reso-
nance of the employed deuterated solvent or proteo impurity of
the solvent; C6D6 (7.16 ppm) and CD2Cl2 (5.32 ppm) for 1H NMR;
C6D6 (128.0 ppm) and CD2Cl2 (54.0 ppm) for 13C NMR. 11B, 31P{1H}
and 195Pt{1H} NMR spectra were referenced using an external stan-
dard of BF3(OEt2) (0.0 ppm), 85% H3PO4 in D2O (0.0 ppm) and 1.2m
Na2[PtCl6] in D2O (0.0 ppm), respectively. Temperature calibration
was performed using a [D4]-methanol sample, as outlined in the
Bruker VTU user manual.
1
1
1
Experimental Section
An argon-filled MBraun UNIlab glove box equipped with a À308C
freezer was employed for the manipulation and storage of the
FcPPB ligand and its complexes, and reactions were performed on
a double manifold high vacuum line using standard techniques.[43]
A Fisher Scientific Ultrasonic FS-30 bath was used to sonicate reac-
tion mixtures where indicated. Residual oxygen and moisture was
removed from the argon stream by passage through an Oxisorb-W
scrubber from Matheson Gas Products.
Herein, numbered proton and carbon atoms refer to the positions
of the C5H4 rings and the phenylene linker within the FcPPB ligand
backbone. The C5H4 ring bound to the C5H4P(tBu)Ar phosphine was
numbered C1’–5’, where C1’ is the ipso-carbon atom bound to phos-
horus, and the C5H4 ring bound to the C5H4PPh2 phosphine was
numbered C1’’–5’’, where C1’’ is the ipso-carbon atom bound to phos-
phorus. Prior to installation of the -BPh2 group, the phenylene
linker was numbered such that C1 refers to the carbon atom
bound to Br, and C2 refers to the carbon atom bound to phosphine
moiety. Following installation of the -BPh2 group, the phenylene
linker was numbered such that C1 refers to the carbon atom
bound to the phosphine moiety, and C2 refers to the carbon atom
bound to the borane. The remainder of the carbon atoms and pro-
tons in the phenylene linker were numbered accordingly in both
cases. Inequivalent phenyl rings on boron and phosphorus are la-
beled A and B so that the proton and carbon resonances belong-
ing to a single phenyl ring can be identified. We did not identify
which P- or B-phenyl rings give rise to the signals labeled A or B,
respectively.
Anhydrous CH2Cl2 was purchased from Aldrich. Hexanes and tolu-
ene were initially dried and distilled at atmospheric pressure from
CaH2 and Na, respectively. Diethyl ether and tetrahydrofuran were
initially dried and distilled at atmospheric pressure from Na/Ph2CO.
Unless otherwise noted, all proteo solvents were stored over an
appropriate drying agent (toluene, benzene, diethyl ether, tetrahy-
drofuran=Na/Ph2CO; hexanes=Na/Ph2CO/tetra-glyme; CH2Cl2 =
CaH2) and introduced to reactions via vacuum transfer with con-
densation at À788C. Deuterated solvents (ACP Chemicals) were
dried over CaH2 (CD2Cl2) or Na/Ph2CO (C6D6).
N,N,N’,N’-Tetramethylethane-1,2-diamine (TMEDA), 1,1,2,2-tetrabro-
moethane, 1,2-dibromobenzene, ClPPh2, HNEt2, 1,3,5,7-cyclooctate-
traene, 1,5-cyclooctadiene, phenylacetylene, styrene, cyclooctene
and 1-octene were purchased from Sigma–Aldrich and stored
under argon following distillation from molecular sieves. HC2C6D5
was purchased from CDN Isotopes and stored under argon.
BF3·Et2O was purchased from Sigma–Aldrich and distilled from
CaH2 prior to use. Bicyclo[2.2.1]hept-2-ene and PCl3 were pur-
chased from Sigma–Aldrich and distilled in vacuo prior to use.
tBuLi solution (1.7m in pentane) was purchased from Sigma–Al-
drich; tBuLi was isolated as a solid and stored under argon. Ferro-
cene, BBr3, nBuLi solution (1.6m in hexanes), tBuMgBr solution
(2.0m in Et2O), HCl solution (4.0m in dioxanes), CNXyl, lithium
metal, magnesium turnings and diphenylacetylene were purchased
from Sigma–Aldrich and either used as was or stored under argon.
SnPh4 was purchased from Eastman Organic Chemicals and used
as was. C6F5Br was purchased from Oakwood Chemicals and dis-
tilled from molecular sieves prior to use. K2PtCl4 was purchased
from Pressure Chemicals and used as was. CO of>99.0% purity
was purchased from Sigma–Aldrich. Argon and C2H4 of 99.999%
purity was purchased from Praxair. H2 of 99.999% purity was pur-
chased from VitalAire. BrBPh2 was prepared from SnPh4 and BBr3
according to the literature procedure.[44] ClP(NEt2)2, which was uti-
lised to prepare (o-BrC6H4)P(NEt2)2, was prepared from PCl3 and
HNEt2 according to the literature procedure.[45] [Fe(h5-C5H4Br)2] was
prepared from [Fe(h5-C5H4Li)2(TMEDA)][46] according to the literature
procedure.[47] [Fe(h5-C5H4Br)(h5-C5H4PPh2)] was prepared from
[Fe(h5-C5H4Br)2] according to the literature procedure.[30] [Pt(nb)3]
was prepared from [PtCl2(COD)][48] according to the literature pro-
cedure.[49] B(C6F5)3 was prepared from C6F5MgBr and BF3·Et2O ac-
cording to the literature procedure.[50]
X-ray crystallographic analyses were performed on suitable crystals
coated in Paratone oil and mounted on a SMART APEX II diffrac-
tometer with a 3 kW Sealed tube Mo generator in the McMaster
Analytical X-Ray (MAX) Diffraction Facility. In all cases, non-hydro-
gen atoms were refined anisotropically and hydrogen atoms were
generated in ideal positions and then updated with each cycle of
refinement, with the only exception being H(46) in 6A·4C6H6,
which was located in the difference map. One molecule of C6H6 in
6A·4C6H6 was positionally disordered over two positions in a 58:42
ratio. The disorder was modeled allowing occupancy and position-
al parameters to refine freely; carbon atoms were restrained to
have similar thermal parameters through the use of the SIMU com-
mand. In all cases a numerical absorption correction was applied.
The crystallographic data are summarised in Table 1.
CCDC 1019205 (FcPPB), 1019206 (1·CH2Cl2), 1019207 (2·2CH2Cl2),
1019208 (3·CH2Cl2) and 1019209 (6A·4C6H6) contain the supple-
mentary crystallographic data for this paper. These data can be ob-
tained free of charge from The Cambridge Crystallographic Data
Centre via www.ccdc.cam.ac.uk/data_request/cif.
(o-BrC6H4)P(NEt2)2: Tetrahydrofuran (50 mL) and diethyl ether
(50 mL) were condensed into a 250 mL two-necked round-bot-
tomed flask using a dry ice/acetone bath, to which 1,2-dibromo-
benzene (6.86 g, 29.1 mmol) in tetrahydrofuran (10 mL) was added
by syringe. The solution was cooled to À110 8C through the use of
a diethyl ether/liquid nitrogen bath, and a solution of nBuLi in hex-
IR spectra were recorded on a Thermo Scientific Nicolet 6700 FTIR
spectrometer (reported stretches are strong unless otherwise
noted). Combustion elemental analyses were performed on
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Table 1. Crystallographic data collection and refinement parameters for FcPPB and compounds 1–3 and 6A.
FcPPB
1·CH2Cl2
2·2CH2Cl2
3·CH2Cl2
6A·4C6H6
formula
C44H41BFeP2
C44H41BFeP2Pt
·CH2Cl2
978.38
100(2)
triclinic
C45H41BFeOP2Pt
·2CH2Cl2
1091.32
100(2)
triclinic
C106H100B2Fe2N2P4Pt2
·2CH2Cl2
2219.11
100(2)
monoclinic
Cc
21.645(3)
12.0075(16)
35.074(5)
90
94.283(3)
90
9090(2)
4
1.621
3.621
4448
C52H47BFeP2Pt
·4C6H6
1308.02
100(2)
monoclinic
P21/n
17.313(3)
19.108(3)
19.095(3)
90
104.823(2)
90
6107(2)
4
1.423
2.622
Mw [gmolÀ1
T [K]
crystal system
space group
a [ꢀ]
b [ꢀ]
c [ꢀ]
a [8]
b [8]
]
698.37
100(2)
triclinic
¯
P1
¯
P1
¯
P1
9.0532(8)
10.3272(9)
19.361(2)
101.061(2)
91.972(2)
102.617(2)
1728.1(3)
2
1.342
0.561
732
0.22ꢂ0.10ꢂ0.08
1.08–28.33
33862
10.787(2)
13.260(2)
14.740(3)
71.759(4)
77.594(3)
83.677(3)
1953.5(6)
2
1.663
4.199
972
0.26ꢂ0.12ꢂ0.04
1.48–31.62
27043
9.897(1)
11.960(2)
19.840(3)
101.204(3)
92.005(2)
109.936(2)
2152.5(5)
2
1.684
3.942
1084
0.21ꢂ0.14ꢂ0.08
1.05–26.29
23370
g [8]
V [ꢁ3]
Z
1calcd [mgmÀ13
]
m [mmÀ1
F(000)
]
2664
crystal size [mm3]
q range [8]
0.19ꢂ0.16ꢂ0.09
1.89–26.45
51591
0.17ꢂ0.08ꢂ0.04
1.62–26.66
82018
reflns collected
independent reflns
completeness to q max [%]
max/min transmission
GOF on F2
8547
99.3
0.9565/0.8865
1.086
12749
97.1
0.8500/0.4081
1.004
8557
98.1
0.7433/0.4915
1.034
11518
99.8
0.7364/0.5462
1.043
12677
98.6
0.9024/0.6641
1.063
final R1 [I>2s(I)] [%]
3.52
3.45
3.47
4.00
4.60
anes (18 mL, 1.6m) was added dropwise over 20 min. The reaction
mixture was maintained at À110 8C for 2 h, after which point a solu-
tion of ClÀP(NEt2)2 (6.13 g, 29.1 mmol) in THF (20 mL) was added
dropwise over 10 min. The reaction mixture was maintained at
À110 8C for an additional hour before warming to room tempera-
ture overnight. The resulting light orange, opaque solution was
evaporated to dryness in vacuo to yield an opaque, orange oil.
Hexanes (100 mL) were added to the crude oil and the resulting
slurry was sonicated and filtered to remove any unwanted LiCl,
which was washed with hexanes (2ꢂ20 mL). The clear and light
yellow filtrate was evaporated to dryness in vacuo to yield a trans-
lucent, fawn yellow oil. Yield=9.26 g (96%); 1H NMR (500 MHz,
[D6]benzene, 258C): d=7.49 (dt, 3J(H,H)=8 Hz, 3J(H,P)=2 Hz, 1H;
CH3), 7.44 (ddd, 3J(H,H)=8 Hz, 4J(H,P)=5 Hz, 4J(H,H)=1 Hz, 1H;
CH6), 7.08 (t, 3J(H,H)=8 Hz, 1H; CH4), 6.78 (tt, 3J(H,H)=8 Hz,
4J(H,H)=2 Hz, 1H; CH5), 3.09–2.94 (m, 8H; N(CH2CH3)2), 1.02 ppm
(t, 3J(H,H)=7 Hz, 12H; N(CH2CH3)2); 13C{1H} NMR (126 MHz,
[D6]benzene, 258C): d=143.9 (d, 2J(C,P)=15 Hz; C2), 134.5 (s; C6),
133.3 (d, 2J(C,P)=6 Hz; C3), 129.9 (s; C5), 128.2 (d, 1J(C,P)=30 Hz;
filtrate was evaporated to dryness in vacuo to yield a translucent,
fawn yellow oil. Yield=6.35 g (91%); 1H NMR (500 MHz,
3
[D6]benzene, 258C): d=7.80 (appt. d, J(H,H)=8 Hz, 1H; CH3), 7.00
3
4
4
(ddd, J(H,H)=8 Hz, J(H,P)=5 Hz, J(H,H)=1 Hz, 1H; CH6), 6.81 (t,
3J(H,H)=8 Hz, 1H; CH4), 6.60 ppm (dt, J(H,H)=8 Hz, J(H,H)=2 Hz,
1H; CH5); 13C{1H} NMR (126 MHz, [D6]benzene, 258C): d=140.2 (d,
1J(C,P)=57 Hz; C2), 134.2 (s; C5), 133.5 (s; C6), 132.4 (d, 2J(C,P)=
5 Hz; C3), 128.9 (s; C4), 127.2 ppm (d, 2J(C,P)=45 Hz; C1); 31P{1H}
NMR (203 MHz, [D6]benzene, 258C): d=153.7 ppm (s); MS calcd for
C6H4BrCl2P: 257.8749 [M+]; found: 257.8601.
3
4
(o-BrC6H4)tBuPCl: Diethyl ether (100 mL) was condensed into
a
250 mL two-necked round-bottomed flask equipped with
a reflux condenser using a dry ice/acetone bath, to which (o-
BrC6H4)PCl2 (6.31 g, 24.5 mmol) in diethyl ether (20 mL) was added
by syringe. The solution was cooled to À208C through the use of
a brine/liquid nitrogen bath, and a solution of tBuMgBr in diethyl
ether (12 mL, 2.0m) was added dropwise over 10 min (the addition
of tBuMgBr resulted in the formation of a white precipitate). The
reaction mixture was maintained at À208C for 30 min and then re-
fluxed for 6 h. The resulting light orange, opaque solution was
evaporated to dryness in vacuo to yield a white/yellow oil. At this
point, the reflux condenser was replaced with a swivel frit and di-
ethyl ether (80 mL) was added to the crude oil; the resulting slurry
was sonicated and filtered to remove any unwanted MgBrCl, which
was washed with diethyl ether (2ꢂ10 mL). The clear, light yellow
filtrate was evaporated to dryness in vacuo to yield a translucent,
fawn yellow oil, which was then distilled in vacuo at 1308C to yield
a clear, colourless oil. Yield=4.71 g (69%); 1H NMR (500 MHz,
[D6]benzene, 258C): d=7.72 (dt, 3J(H,H)=8 Hz, 4J(H,P)=2 Hz, 1H;
CH6), 7.22 (ddd, 3J(H,H)=8 Hz, 3J(H,P)=4 Hz, 4J(H,H)=1 Hz, 1H;
CH3), 6.90 (dt, 3J(H,H)=8 Hz, 4J(H,H)=1 Hz, 1H; CH5), 6.66 (t,
3J(H,H)=7 Hz, 1H; CH4), 1.02 ppm (d, 3J(H,P)=13 Hz, 9H; CMe3);
13C{1H} NMR (126 MHz, [D6]benzene, 258C): d=137.3 (d, 1J(C,P)=
46 Hz; C2), 134.5 (s; C6), 133.0 (d, 2J(C,P)=1 Hz; C3), 131.7 (s; C4),
129.6 (d, 2J(C,P)=42 Hz; C1), 127.2 (s; C5), 36.4 (d, 1J(C,P)=33 Hz;
2
C1), 127.6 (s; C4), 44.7 (d, J(C,P)=19 Hz; N(CH2CH3)2), 15.8 ppm (d,
3J(C,P)=3 Hz; N(CH2CH3)2); 31P{1H} NMR (203 MHz, [D6]benzene,
258C): d=96.4 ppm (s); MS calcd for C14H24BrN2P: 331.2217 [M+];
found: 332.0854.
(o-BrC6H4)PCl2: Tetrahydrofuran (200 mL) was condensed into
a 500 mL two-necked round-bottomed flask using a dry ice/ace-
tone bath, to which
a solution of (o-BrC6H4)P(NEt2)2 (9.01 g,
27.2 mmol) in tetrahydrofuran (20 mL) was added by syringe. A so-
lution of HCl in dioxanes (54 mL, 4.0m) was then added dropwise
at room temperature, which resulted in the immediate formation
of a white precipitate; the reaction mixture was left to stir for 1 h
at room temperature. Next, the reaction mixture was evaporated
to dryness in vacuo to yield an opaque, white oil. Diethyl ether
(80 mL) was added to the crude oil and the resulting slurry was so-
nicated and filtered to remove any unwanted HCl·HNEt2, which
was washed with diethyl ether (1ꢂ20 mL). The clear and colourless
Chem. Eur. J. 2014, 20, 1 – 15
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9
ꢀ 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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CMe3), 25.8 ppm (d, 2J(C,P)=17 Hz, CMe3); 31P{1H} NMR (203 MHz,
[D6]benzene, 258C): d=105.5 ppm (s); MS calcd for C10H13BrClP:
279.5337 [M+]; found: 279.9598.
ing slurry was sonicated, which resulted in the precipitation of
FcPPB as a light yellow solid. The hexanes solution was filtered,
and the collected FcPPB ligand was washed with hexanes (2ꢂ
10 mL). Yield=1.36 g (78%); 1H NMR (600 MHz, [D6]benzene,
258C): d=7.95 (brd, 3J(H,H)=5 Hz, 2H; o-BPh2 A), 7.86 (brd,
[Fe(h5-C5H4PPh2){h5-C5H4P(tBu)(o-BrC6H4)}]·0.4pentane: Tetrahy-
drofuran (125 mL) was condensed into a 250 mL two-necked
round-bottomed flask containing [Fe(h5-C5H4Br)(h5-C5H4PPh2)]
(3.62 g, 8.07 mmol) through the use of a dry ice/acetone bath. The
tetrahydrofuran solution was cooled to À788C and a solution of
nBuLi in hexanes (5.0 mL, 1.6m) was added dropwise, causing the
transparent, orange solution to turn crimson red. The reaction mix-
ture was left to stir at À788C for 2 h, after which a solution of (o-
BrC6H4)P(tBu)Cl (2.26 g, 8.07 mmol) in tetrahydrofuran (10 mL) was
added dropwise. The reaction mixture was then left to stir over-
night at room temperature. After stirring overnight the transpar-
ent, crimson red solution was evaporated to dryness in vacuo to
yield a bright red oil. Hexanes (100 mL) was added to the oil and
the resulting slurry was sonicated, which resulted in the precipita-
tion of LiCl. The hexanes solution was filtered to remove LiCl and
the filtrate was evaporated to dryness in vacuo to again yield an
orange/red oil. The crude oil was brought into the dry box and re-
crystallised from pentane, which yielded [Fe(h5-C5H4PPh2){h5-C5H4P-
(tBu)(o-BrC6H4)}]·0.4pentane as an orange/yellow solid. Yield=
3
3J(H,H)=5 Hz, 2H; o-BPh2 B), 7.82 (d, J(H,H)=7 Hz, 1H; CH3), 7.42
(ddt, 3J(H,H)=7 Hz, 4J(H,H)=3 Hz, 5J(H,P)=1 Hz, 1H; CH4), 7.39–
7.36 (m, 2H; o-PPh2 A), 7.31–7.28 (m, 4H; o-BPh2 B, m-BPh2 A), 7.23
(appt. tt, 3J(H,H)=8 Hz, 2J(H,P)=1 Hz, 3H; m-BPh2 B, CH6), 7.19
(ddt, 3J(H,H)=7 Hz, 4J(H,P)=3 Hz, 4J(H,H)=1 Hz, 1H; CH5), 7.15–
7.12 (m, 2H; p-BPh2 A+B), 7.06 (dt, 3J(H,H)=3 Hz, 4J(H,H)=1 Hz,
3H; m+p-PPh2 A), 7.02–7.01 (m, 3H; m+p-PPh2 B), 4.34 (sextet,
3J(H,H)=1 Hz, 1H; CH2’/5’), 4.25 (sextet, 3J(H,H)=1 Hz, 1H; CH4’/3’),
3
3
4.12 (septet, J(H,H)=1 Hz, 1H; CH3’/4’), 4.08 (sextet, J(H,H)=1 Hz,
1H; CH5’/2’), 3.59 (septet, 3J(H,H)=1 Hz, 1H; CH2’’/5’’), 3.43 (sextet,
3J(H,H)=1 Hz, 1H; CH5’’/2’’), 3.29 (sextet, J(H,H)=1 Hz, 1H; CH3’’/4’’),
3
3.22 (sextet, J(H,H)=1 Hz, 1H; CH4’’/3’’), 0.76 ppm (d, J(H,P)=14 Hz,
3
3
9H; CMe3); 13C{1H} NMR (151 MHz, [D6]benzene, 258C): d=164.9
(brd, J(C,P)=43 Hz; C2), 149.5 (brs; ipso-BPh2 A or B), 148.2 (brs;
2
ipso-BPh2 A or B), 140.0 (d, 1J(C,P)=12 Hz; ipso-PPh2 B), 139.2 (d,
1J(C,P)=12 Hz; ipso-PPh2 A), 135.7 (d, 1J(C,P)=45 Hz; C1), 134.8
(brs; o-BPh2 B), 134.2 (d, 2J(C,P)=20 Hz; o-PPh2 A), 133.7 (d,
2J(C,P)=20 Hz; o-PPh2 B), 133.4 (brs; o-BPh2 A), 132.0 (s; C4), 131.9
(s; C3), 129.3 (s; m-BPh2 B), 128.4 (s; p-PPh2 A), 128.4 (d, 3J(C,P)=
1
3.83 g (74%); H NMR (600 MHz, [D6]benzene, 258C): d=7.47 (dd,
3J(P,H)=4 Hz, 3J(H,H)=1 Hz, 1H; CH3), 7.46–7.43 (m, 4H; o-PPh2),
7.42 (d, 3J(H,H)=2 Hz, 1H; CH6), 7.07–7.03 (m, 6H; m+p-PPh2), 6.87
3
7 Hz; m-PPh2 A), 128.3 (d, J(C,P)=7 Hz; m-PPh2 B), 128.2 (s; p-PPh2
3
B), 127.6 (s; m-BPh2 A, C6), 127.5 (d, J(C,P)=6 Hz; C5), 126.9 (brs; p-
3
4
3
(dt, J(H,H)=8 Hz, J(H,H)=1 Hz, 1H; CH5), 6.71 (ddt, J(H,H)=8 Hz,
4J(H,P)=2 Hz, 4J(H,H)=1 Hz, 1H; CH4), 4.35 (septet, 3J(H,H)=1 Hz,
1H; CH5’/2’), 4.23 (sextet, 3J(H,H)=1 Hz, 1H; CH3’’/4’’), 4.20 (septet,
3J(H,H)=1 Hz, 1H; CH4’/3’), 4.15 (sextet, 3J(H,H)=1 Hz, 1H; CH3’/4’),
4.15–4.13 (m, 2H; CH2’’/5’’, CH4’’/3’’), 4.04 (sextet, 3J(H,H)=1 Hz, 1H;
CH2’/5’), 3.87 (octet, 3J(H,H)=1 Hz, 1H; CH5’’/2’’), 1.10 ppm (d,
3J(H,P)=12 Hz, 9H; CMe3); 13C{1H} NMR (151 MHz, [D6]benzene,
258C): d=140.0 (appt. t, 1J(C,P)=12 Hz; ipso-PPh2), 139.7 (d,
2J(C,P)=22 Hz; C1), 137.1 (s; C6), 134.0 (appt. t, 2J(C,P)=20 Hz; o-
PPh2), 133.4 (d, 2J(C,P)=3 Hz; C3), 133.2 (d, 1J(C,P)=40 Hz; C2),
1
BPh2 A or B), 126.1 (brs; p-BPh2 A or B), 77.7 (d, J(C,P)=8 Hz; C1’’),
2
2
75.9 (d, J(C,P)=20 Hz; C2’/5’), 74.5 (s; C3’’/4’’), 74.4 (d, J(C,P)=14 Hz;
C
2’’/5’’), 73.8 (s; C4’’/3’’), 73.6 (d, J(C,P)=3 Hz; C5’’/2’’), 73.5 (d, J(C,P)=
2
2
10 Hz; C5’/2’), 72.8 (s; C4’/3’), 72.4 (d, 3J(C,P)=9 Hz; C3’/4’), 70.6 (d,
1J(C,P)=16 Hz; C1’), 34.2 (d, 1J(C,P)=7 Hz; CMe3), 27.4 ppm (d,
2J(C,P)=4 Hz; CMe3); 31P{1H} NMR (203 MHz, [D6]benzene, 258C):
d=19.7 (s; C5H4P(tBu)Ar), À17.2 ppm (s; C5H4PPh2); 11B NMR
(161 MHz, [D6]benzene, 258C): d=17 ppm (brs, w1/2 =1300 Hz); el-
emental analysis calcd (%) for C44H41BFeP2: C 75.67, H 5.92; found:
C 75.70, H 6.12.
3
3
130.5 (s; C4), 128.7 (d, J(C,P)=4 Hz; p-PPh2), 128.5 (appt. t, J(C,P)=
6 Hz; m-PPh2), 126.4 (s; C5), 77.4 (d, 1J(C,P)=9 Hz; C1’’), 76.3 (d,
[Pt(FcPPB)]·0.3hexanes (1): Toluene (50 mL) was condensed into
a round-bottomed flask containing [Pt(nb)3] (351 mg, 0.734 mmol)
and FcPPB (513 mg, 0.734 mmol) through the use of a dry ice/ace-
tone bath. The fawn yellow reaction solution was left to stir for 5 h
at room temperature before being evaporated to dryness in vacuo.
Hexanes (50 mL) were condensed into the reaction flask and the
oily suspension was sonicated for 15 min, after which point the
hexanes solution was filtered and the product was collected as
a fawn yellow solid. The collected product was washed with hex-
anes (2ꢂ10 mL) Yield=515 mg (76%); 1H NMR (600 MHz,
1J(C,P)=22 Hz; C1’), 76.2 (d, J(C,P)=28 Hz; C5’/2’), 74.5 (d, J(C,P)=
3
2
2
16 Hz; C2’’/5’’), 74.1 (d, J(C,P)=14 Hz; C5’’/2’’), 73.5 (s; C3’’/4’’), 73.3 (s;
C
4’’/3’’), 73.2 (d, 2J(C,P)=4 Hz; C2’/5’), 72.8 (s; C3’/4’), 72.0 (d, 2J(C,P)=
6 Hz; C4’/3’), 32.6 (d, 1J(C,P)=16 Hz; CMe3), 28.5 ppm (d, 2J(C,P)=
16 Hz; CMe3); 31P{1H} NMR (203 MHz, [D6]benzene, 258C): d=4.9 (s;
C5H4P(tBu)Ar), À17.0 ppm (s; C5H4PPh2); elemental analysis calcd
(%) for C34H35.8BrFeP2: C 63.59, H 5.62; found: C 63.50, H 5.75.
FcPPB: Toluene (120 mL) was condensed into a 250 mL round-bot-
tomed
flask
containing
[Fe(h5-C5H4PPh2){h5-C5H4P(tBu)(o-
3
BrC6H4)}]·0.4pentane (1.54 g, 2.40 mmol) through the use of a dry
ice/acetone bath. The toluene solution was cooled to À458C and
a solution of tBuLi (0.32 g, 5.0 mmol) in toluene (5 mL) was added
dropwise. The reaction mixture was then warmed to 08C and left
to stir at that temperature for 3.5 h, during which time a fine,
white solid precipitated from solution, turning the previously trans-
parent, orange solution translucent. The reaction mixture was then
cooled to À458C and a solution of BrÀBPh2 (0.61 g, 2.5 mmol) in
toluene (5 mL) was added dropwise; the reaction mixture was then
left to stir overnight at room temperature. After stirring overnight
the opaque, tangerine coloured solution was evaporated to dry-
ness in vacuo to yield a red/orange oil. The crude oil was brought
into the dry box, at which point toluene (30 mL) was added to pre-
cipitate out LiBr. The crude mixture was centrifuged to separate
LiBr from the desired FcPPB ligand, and the clear orange mother
liquors were evaporated to dryness in vacuo to again yield a red/
orange oil. Hexanes (50 mL) were added to the oil and the result-
[D2]methylene chloride, 258C): d=8.01 (d, J(H,H)=7 Hz, 1H; CH6),
3
7.94 (brs, 2H; o-PPh2 A), 7.62 (d, J(H,H)=7 Hz, 2H; o-BPh2 A), 7.53
3
(s, 3H; m+p-PPh2 A), 7.49 (t, J(H,H)=7 Hz, 1H; CH5), 7.28–7.22 (m,
3H; m+p-PPh2 B), 7.16–7.12 (m, 3H; CH4, m-BPh2 A), 7.00 (t,
3
3J(H,H)=7 Hz, 1H; p-BPh2 A), 6.90 (t, J(H,H)=8 Hz, 1H; CH3), 6.79
3
3
(t, J(H,H)=9 Hz, 2H; o-PPh2 B), 6.65 (t, J(H,H)=7 Hz, 2H; m-BPh2
3
3
B), 6.19 (t, J(H,H)=7 Hz, 1H; p-BPh2 B), 6.10 (t, J(H,H)=5 Hz, 2H;
o-BPh2 B), 4.60 (s, 1H; CH5’/2’), 4.36 (s, 1H; CH5’’/2’’), 4.33 (s, 1H;
CH4’’/3’’), 4.27 (s, 1H; CH3’/4’), 4.23 (s, 1H; CH4’/3’), 4.16 (s, 1H; CH3’’/4’’),
3.93 (s, 1H; CH2’/5’), 3.79 (s, 1H; CH2’’/5’’), 1.07 ppm (d, J(H,P)=12 Hz,
3
9H; CMe3); 13C{1H} NMR (151 MHz, [D2]methylene chloride, 258C):
d=161.9 (brd, J(C,P)=38 Hz; C2), 149.6 (appt. brd, J=15 Hz; ipso-
2
BPh2 A), 148.0 (dd, 1J(C,P)=50 Hz, 3J(C,P)=13 Hz; C1), 137.3 (d,
1J(C,P)=41 Hz; ipso-PPh2 A), 136.1 (d, 2J(C,P)=16 Hz; o-PPh2 A),
134.9 (dd, 1J(C,P)=35 Hz, J(C,P)=4 Hz; ipso-PPh2 B), 134.3 (s; C3),
3
133.9 (dd, 2J(C,P)=28 Hz, 4J(C,P)=3 Hz; C6), 132.3 (d, 2J(C,P)=
13 Hz; o-PPh2 B), 132.2 (s; o-BPh2 A), 131.1 (s; p-PPh2 A), 129.9 (s;
&
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Chem. Eur. J. 2014, 20, 1 – 15
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ꢀ 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÝÝ These are not the final page numbers!

Full Paper
C5), 129.7 (s; m-BPh2 B), 129.0 (s; p-PPh2 B), 129.0 (appt. s; m-PPh2
A), 128.0 (d, 3J(C,P)=10 Hz; m-PPh2 B), 126.9 (s; m-BPh2 A), 125.9
O); elemental analysis calcd (%) for C45H41BFeOP2Pt: C 58.65, H
4.49; found: C 57.94, H 4.68.
4
(appt. d, J=5 Hz; p-BPh2 B), 125.3 (d, J(C,P)=7 Hz; C4), 124.7 (s; p-
[Pt(CNXyl)(FcPPB)] (3): A solution of XylNC (15.4 mg, 0.118 mmol)
in CH2Cl2 (3 mL) was added dropwise at room temperature to a so-
lution of [Pt(FcPPB)]·0.3 hexanes (105 mg, 0.114 mmol) in CH2Cl2
(10 mL). The transparent, orange/red solution was left to stir for
one hour at room temperature before being evaporated to dryness
in vacuo. Hexanes (20 mL) were added to the remaining orange/
red oily residue and the resulting solution was sonicated for
15 min, which resulted in the precipitation of [Pt(CNXyl)(FcPPB)] as
a yellow powder. The hexanes solution was filtered and the collect-
ed product was washed with hexanes (2ꢂ10 mL). Yield=101 mg
BPh2 A), 114.2 (brs; ipso-BPh2 B), 113.5 (brs; o-BPh2 B), 83.7 (d,
1J(C,P)=45 Hz; C1’), 82.7 (d, 1J(C,P)=51 Hz; C1’’), 76.3 (d, 2J(C,P)=
13 Hz; C2’/5’), 74.7 (d, 2J(C,P)=13 Hz; C2’’/5’’), 74.5 (d, 3J(C,P)=8 Hz;
3
2
C
5’’/2’’), 72.9 (d, J(C,P)=3 Hz; C5’/2’), 71.5 (d, J(C,P)=7 Hz; C3’/4’), 71.2
(d, 3J(C,P)=4 Hz; C4’’/3’’), 70.1 (d, 2J(C,P)=6 Hz; C3’’/4’’), 69.9 (d,
3J(C,P)=3 Hz; C4’/3’), 37.1 (d, 1J(C,P)=26 Hz; CMe3), 29.7 ppm (d,
2J(C,P)=6 Hz; CMe3); 31P{1H} NMR (243 MHz, [D6]benzene, 258C):
d=50.8 (d, 1J(P,Pt)=5651 Hz, 2J(P,P)=56 Hz; C5H4P(tBu)Ar),
28.5 ppm (d, 1J(P,Pt)=4183 Hz, 2J(P,P)=56 Hz; C5H4PPh2); 31P{1H}
1
NMR (203 MHz, [D2]methylene chloride, 258C): d=51.3 (d, J(P,Pt)=
1
3
(87%). H NMR (600 MHz, [D6]benzene, 258C): d=8.26 (d, J(H,H)=
5657 Hz, 2J(P,P)=55 Hz; C5H4P(tBu)Ar), 28.4 ppm (d, 1J(P,Pt)=
3
3
7 Hz, 2H; o-BPh2 A), 8.01 (dt, J(H,P)=10 Hz, J(H,H)=1 Hz, 2H; o-
4157 Hz,
2J(P,P)=55 Hz;
C5H4PPh2);
11B NMR
(161 MHz,
PPh2 A), 7.73 (d, J(H,P)=8 Hz, 1H; CH6), 7.54 (d, J(H,H)=7 Hz, 2H;
3
3
[D2]methylene chloride, 258C): d=21 ppm (brs, w1/2 =1400 Hz);
195Pt{1H} NMR (128 MHz, [D2]methylene chloride, 258C): d=
À4934 ppm (dd, 1J(Pt,P)=5654 Hz, 1J(Pt,P)=4138 Hz); elemental
analysis calcd (%) for C45.8H44.2BFeP2Pt: C 59.84, H 4.96; found: C
59.93, H 5.27.
3
o-BPh2 B), 7.30 (t, J(H,H)=8 Hz, 2H; m-BPh2 A), 7.22–7.13 (m, 6H;
CH3, CH5, o-PPh2 B, m-BPh2 B), 7.08–7.03 (m, 5H; CH4, m-PPh2 A, p-
BPh2 A and B), 7.00–6.96 (m, 3H; m-PPh2 B, p-PPh2 A), 6.91 (tq,
3J(H,H)=7 Hz, 4J(H,H)=1 Hz, 1H; p-PPh2 B), 6.65 (t, 3J(H,H)=8 Hz,
3
3
1H; p-Xyl), 6.55 (d, J(H,H)=8 Hz, 2H; m-Xyl), 4.79 (septet, J(H,H)=
1 Hz, 1H; CH2’/5’), 4.52 (s, 1H; CH5’/2’), 4.22 (sextet, 3J(H,H)=1 Hz,
[Pt(CO)(FcPPB)] (2):
A solution of [Pt(FcPPB)] · 0.3 hexanes
1H; CH5’’/2’’), 3.95 (t, J(H,H) 2 Hz, 1H; CH3’/4’), 3.89 (sextet, J(H,H)=
3
3
(64.7 mg, 7.04ꢂ10À2 mmol) in CH2Cl2 (5 mL) was subject to three
freeze/pump/thaw cycles before being cooled to À1408C, at which
point CO was added. The reaction mixture was stirred for one hour
at room temperature before being evaporated to dryness in vacuo
to yield a brown/yellow oily residue. Hexanes (20 mL) were added
to the crude product and the resulting solution was sonicated for
15 min, after which point the resulting solution was evaporated to
dryness in vacuo to yield a mustard yellow solid. Yield=38 mg
1 Hz, 1H; CH4’’/3’’), 3.87 (sextet, 3J(H,H)=1 Hz, 1H; CH4’/3’), 3.81
(sextet, J(H,H)=1 Hz, 1H; CH3’’/4’’), 3.77 (septet, J(H,H)=1 Hz, 1H;
CH2’’/5’’), 1.89 ppm (s, 6H; Xyl-CH3), 1.47 (d, 3J(H,P)=15 Hz, 9H;
CMe3); 13C{1H} NMR (151 MHz, [D6]benzene, 258C): d=170.3 (brd,
2J(C,P)=58 Hz; C2), 163.9 (d, 1J(C,P)=112 Hz ; C1), 158.7 (brs; ipso-
3
3
1
BPh2 A), 149.5 (brs; ipso-BPh2 B), 138.6 (d, J(C,P)=30 Hz; ipso-PPh2
B), 138.0 (s; o-BPh2 B), 137.0 (s; o-BPh2 A), 136.6 (d, J(C,P)=27 Hz;
1
2
2
ipso-PPh2 A), 135.6 (d, J(C,P)=15 Hz; o-PPh2 A), 134.7 (dd, J(C,P)=
1
3
(58%); H NMR (600 MHz, [D6]benzene, 258C): d=8.12 (d, J(H,H)=
27 Hz, J(C,P)=5 Hz; C6), 134.1 (s; o-Xyl), 133.4 (d, J(C,P)=15 Hz; o-
4
2
3
7 Hz, 2H; o-BPh2 A), 7.83–7.80 (m, 2H; o-PPh2 A), 7.66 (d, J(H,P)=
PPh2 B), 131.1 (s; C5), 130.4 (s; C3), 130.4 (s; p-PPh2 A), 129.1 (s; p-
8 Hz, 1H; CH6), 7.47 (t, 3J(H,H=8 Hz, 2H; m-BPh2 A), 7.35 (t,
3J(H,H)=7 Hz, 1H; CH3), 7.30–7.28 (m, 3H; o-BPh2 B, p-BPh2 A),
7.18–7.12 (m, 3H; CH5, o-PPh2 B), 7.08–7.05 (m, 1H; CH4), 7.04–7.00
(m, 3H; m+p-PPh2 A), 6.89–6.83 (m, 4H; p-BPh2 B, m+p-PPh2 B),
6.64 (t, 3J(H,H)=8 Hz, 2H; m-BPh2 B), 4.51 (s, 1H; CH5’/2’), 4.49 (d,
3J(H,H)=1 Hz, 1H; CH2’/5’), 4.03–4.01 (m, 1H; CH2’’/5’’), 4.01–4.00 (m,
1H; CH5’’/2’’), 3.91 (sextet, 3J(H,H)=1 Hz, 1H; CH3’’/4’’), 3.85 (sextet,
3J(H,H)=1 Hz, 1H; CH4’/3’), 3.81 (q, 3J(H,H)=2 Hz, 1H; CH3’/4’), 3.73
PPh2 B), 128.8 (s; ipso-Xyl), 128.2 (s; C4), 128.1 (d, J(C,P)=9 Hz; m-
3
3
PPh2 A), 127.9 (d, J(C,P)=10 Hz; m-PPh2 B), 127.6 (s; m-Xyl), 127.4
(s; p-Xyl), 126.8 (s; m-BPh2 A), 126.6 (s; m-BPh2 B), 124.6 (s; p-BPh2
1
1
B), 124.0 (s; p-BPh2 A), 86.1 (d, J(C,P)=36 Hz; C1’’), 85.7 (d, J(C,P)=
8 Hz; C1’), 75.4 (d, 2J(C,P)=13 Hz; C2’’/5’’), 75.0 (d, 2J(C,P)=13 Hz;
C
2’/5’), 74.4 (d, 3J(C,P)=5 Hz; C5’’/2’’), 73.4 (s; C5’/2’), 71.0 (d, 2J(C,P)=
7 Hz; C3’/4’), 70.2 (d, 2J(C,P)=5 Hz; C3’’/4’’), 69.8 (d, 3J(C,P)=2 Hz;
4’’/3’’), 69.7 (d, 3J(C,P)=2 Hz; C4’/3’), 36.8 (d, 1J(C,P)=34 Hz; CMe3),
30.4 (d, 2J(C,P)=5 Hz; CMe3), 18.5 ppm (s; Xyl-CH3); 31P{1H} NMR
C
3
3
(sextet, J(H,H)=1 Hz, 1H; CH4’’/3’’), 1.31 ppm (d, J(H,P)=15 Hz, 9H;
CMe3); 13C{1H} NMR (151 MHz, [D6]benzene, 258C): d=193.6 (dd,
1
2
(203 MHz, [D6]benzene, 258C): d=62.7 (d, J(P,Pt)=4549 Hz, J(P,P)
11 Hz ; C5H4P(tBu)Ar), 21.8 ppm (d, 1J(Pt,P)=1381 Hz, 2J(P,P) 11 Hz;
C5H4PPh2); 11B NMR (161 MHz, [D6]benzene, 258C): d=13 (brs, w1/
2 =800 Hz); 11B NMR (161 MHz, [D2]methylene chloride, 258C): d=
10 (brs, w1/2 =800 Hz); 195Pt{1H} NMR (128 MHz, [D6]benzene, 258C):
2J(C,P)=87 Hz, J(C,P)=9 Hz; Pt-CO), 165.5 (brd, J(C,P)=45 Hz; C2),
153.0 (brs; ipso-BPh2 A), 140.1 (s; o-BPh2 B), 138.9 (dd, 1J(C,P)=
49 Hz, 3J(C,P)=11 Hz; C1), 138.4 (d, 1J(C,P)=32 Hz; ipso-PPh2 B),
2
2
1
136.9 (s; o-BPh2 A), 136.2 (d, J(C,P)=36 Hz; ipso-PPh2 A), 135.2 (d,
2J(C,P)=15 Hz; o-PPh2 A), 134.5 (d, 2J(C,P)=26 Hz; C6), 132.9 (d,
2J(C,P)=14 Hz; o-PPh2 B), 130.9 (s; C3), 130.5 (d, 2J(C,P)=9 Hz; m-
PPh2 A), 130.3 (brs; ipso-BPh2 B), 129.0 (s; p-PPh2 B), 128.2 (s; C5, p-
PPh2 A), 128.1 (s; p-BPh2 B), 127.7 (d, 3J(C,P)=10 Hz; m-PPh2 B),
127.3 (s; m-BPh2 A), 126.0 (s; m-BPh2 B), 125.7 (s; p-BPh2 A), 125.3
(d, 4J(C,P)=7 Hz; C4), 86.9 (dd, 1J(C,P)=36 Hz, 3J(C,P)=6 Hz; C1’),
86.0 (d, 1J(C,P)=41 Hz; C1’’), 75.4 (d, 2J(C,P)=7 Hz; C5’/2’), 75.0 (s;
d=À4486 ppm (brdd, 1J(Pt,P)=4632 Hz, 1J(Pt,P)=1430 Hz, w1/2
=
300 Hz); IR (CH2Cl2): n˜ =2128 cmÀ1 (CꢀN); IR (nujol): n˜ =2122 cmÀ1
(CꢀN); elemental analysis calcd (%) for C53H50BFeNP2Pt: C 62.12; H
4.92; N 1.37; found: C 62.52, H 5.07, N 1.20.
[PtH(m-H)(FcPPB)] (4): A solution of [Pt(FcPPB)] · 0.3 hexanes
(25.0 mg, 2.72ꢂ10À2 mmol) in [D6]benzene (1 mL) was subject to
three freeze/pump/thaw cycles; H2 was then added to the reaction
mixture at room temperature, which resulted in the in situ genera-
tion of [PtH(m-H)(FcPPB)]. 1H NMR (600 MHz, [D6]benzene, 258C):
d=8.21 (d, 3J(H,H)=7 Hz, 2H; o-BPh2 A), 8.09 (dd, 3J(H,P)=11 Hz,
C
3’’/4’’), 74.8 (d, 2J(C,P)=20 Hz; C2’’/5’’), 72.1 (d, 2J(C,P)=8 Hz; C5’’/2’’),
71.5 (d, 2J(C,P)=7 Hz; C2’/5’), 70.1 (d, 3J(C,P)=4 Hz; C3’/4’), 69.2 (s;
C4’’/3’’), 69.0 (d, 3J(C,P)=4 Hz; C4’/3’), 37.9 (d, 1J(C,P)=31 Hz; CMe3),
29.4 ppm (d, 2J(C,P)=6 Hz; CMe3); 31P{1H} NMR (203 MHz,
[D6]benzene, 258C): d=59.4 (s, 1J(P,Pt)=4884 Hz; C5H4P(tBu)Ar),
22.8 ppm (s, 1J(Pt,P)=2343 Hz; C5H4PPh2); 11B NMR (161 MHz,
[D6]benzene, 258C): d=21 ppm (brs, w1/2 =1550 Hz); 11B NMR
3
3J(H,H)=7 Hz, 2H; o-PPh2 A), 7.72 (d, J(H,H)=7 Hz, 1H; CH6), 7.61
3
3
(d, J(H,H)=7 Hz, 2H; o-BPh2 B), 7.48 (t, J(H,H)=7 Hz, 2H; m-BPh2
3
A), 7.31 (t, J(H,H)=7 Hz, 1H; p-BPh2 A), 7.29–7.24 (m, 3H; m+p-
3
3
(161 MHz, [D2]methylene chloride, 258C): d=19 ppm (brs, w1/2
=
BPh2 B), 7.08 (t, J(H,H)=7 Hz, 1H; CH5), 7.04 (t, J(H,H)=7 Hz, 1H;
1550 Hz); 195Pt{1H} NMR (128 MHz, [D2]methylene chloride, 258C):
d=À4422 ppm (dd, 1J(Pt,P)=4820 Hz, 1J(Pt,P)=2223 Hz); IR
(CH2Cl2): n˜ =1982 cmÀ1 (CꢀO); IR (nujol): n˜ =1994, 1968 cmÀ1 (Cꢀ
CH4), 7.01–6.95 (m, 6H; m+p-PPh2 A and B), 6.91 (t, J(H,H)=7 Hz,
3
1H; CH3), 6.87 (dd, 3J(H,P)=13 Hz, 3J(H,H)=7 Hz, 2H; o-PPh2 B),
4.76 (s, 1H; CH2’/5’), 4.45 (s, 1H; CH2’’/5’’), 4.37 (s, 1H; CH5’/2’), 3.96 (s,
Chem. Eur. J. 2014, 20, 1 – 15
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11
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Full Paper
1H; CH3’’/4’’), 3.94 (s, 1H; CH3’/4’), 3.75 (s, 1H; CH4’/3’), 3.59 (s, 1H;
CH4’’/3’’), 3.56 (s, 1H; CH5’’/2’’), 1.30 (d, 3J(H,P)=14 Hz, 9H; CMe3),
zene/hexanes and cooling to À308C. Elemental analysis calcd (%)
for C52H47BFeNP2Pt (6A/6B): C 62.73; H 4.76; found: C 62.48, H
4.73.
1
2
2
À2.76 (dd, J(H,Pt)=792 Hz, J(H,P)=95 Hz, J(H,P)=10 Hz, 1H; Pt-
H-B), À5.19 ppm (ddd, 1J(H,Pt)=905 Hz, 2J(H,P)=177 Hz, 2J(H,P)=
24 Hz, 2J(H,H)=2 Hz, 1H; Pt-H); 13C{1H} NMR (151 MHz,
[D6]benzene, 258C): d=165.0 (brs; C2), 154.6 (brs; ipso-BPh2 A),
148.8 (brs; ipso-BPh2 B), 138.5 (d, 1J(C,P)=48 Hz; C1), 138.5 (s; o-
BPh2 B), 136.6 (s; o-BPh2 A), 135.8 (d, 2J(C,P)=13 Hz; o-PPh2 A),
NMR data for 6A: 1H NMR (600 MHz, [D6]benzene, 258C): d=8.32
(d, 3J(H,H)=8 Hz, 2H; o-BPh), 8.11 (dd, 3J(H,P)=11 Hz, 3J(H,H)=
8 Hz, 2H; o-PPh2 A), 7.72 (d, 3J(H,H)=8 Hz, 1H; CH6), 7.51 (t,
3
3J(H,H)=8 Hz, 2H; m-BPh), 7.32 (t, J(H,H)=7 Hz, 1H; p-BPh), 7.22
3
3
3
(dd, J(H,P)=11 Hz, J(H,H)=8 Hz, 2H; o-PPh2 B), 7.14 (d, J(H,H)=
8 Hz, 2H; o-Pha), 7.08–7.03 (m, 3H; m-PPh2 A, CH5), 6.98 (dt,
1
2
135.8 (d, J(C,P)=60 Hz; ipso-PPh2 A), 135.0 (d, J(C,P)=18 Hz; C6),
134.1 (d, 1J(C,P)=60 Hz; ipso-PPh2 B), 133.6 (d, 2J(C,P)=14 Hz; o-
PPh2 B), 132.5 (s; C4), 131.2 (s; p-PPh2 A), 130.4 (s; C5), 130.1 (s; p-
PPh2 B), 128.1 (d, 3J(C,P)=11 Hz; m-PPh2 A), 127.8 (d, 3J(C,P)=
12 Hz; m-PPh2 B), 127.6 (s; m-BPh2 A), 127.1 (s; m-BPh2 B), 125.7 (s;
p-BPh2 A and B), 124.9 (d, 3J(C,P)=6 Hz; C3), 88.3 (dd, 1J(C,P)=
58 Hz, 3J(C,P)=7 Hz; C1’’), 80.7 (d, 1J(C,P)=40 Hz; C1’), 77.1 (d,
3J(C,P)=10 Hz; C5’’/2’’), 75.0 (d, 3J(C,P)=10 Hz; C2’’/5’’), 74.8 (s; C2’/5’),
74.7 (s; C5’/2’), 73.3 (d, 2J(C,P)=8 Hz; C3’/4’), 70.4 (d, 2J(C,P)=6 Hz;
3J(H,H)=7 Hz, J(H,P)=1 Hz, 1H; p-PPh2 A), 6.91–6.87 (m, 6H; m+
5
p-Pha, o-Phb, CH4), 6.78 (t, 3J(H,H)=7 Hz, 1H; CH3), 6.63 (dt,
3J(H,H)=7 Hz, J(H,P)=1 Hz, 1H; p-PPh2 B), 6.60–6.56 (m, 3H; m+
5
p-Phb), 6.54 (dt, 3J(H,H)=8 Hz, 4J(H,P)=2 Hz, 2H; m-PPh2 B), 5.86
(dd, 2J(H,Pt)=46 Hz, 3J(H,P)=10 Hz, 3J(H,P)=5 Hz, 1H; vinylCb-H),
4.99 (s, 1H; CH2’/5’), 4.65 (s, 1H; CH2’’/5’’), 4.45 (s, 1H; CH5’/2’), 4.43 (s,
1H; CH5’’/2’’), 4.05 (s, 1H; CH3’/4’), 4.04 (s, 1H; CH4’’/3’’), 4.03 (s, 1H;
3
CH3’’/4’’), 3.91 (s, 1H; CH4’/3’), 0.97 ppm (d, J(H,P)=15 Hz, 9H; CMe3);
2
1
C3’’/4’’), 69.6 (s; C4’/3’), 68.7 (d, J(C,P)=6 Hz; C4’’/3’’), 35.0 (d, J(C,P)=
30 Hz; CMe3), 29.7 ppm (d, 2J(C,P)=5 Hz; CMe3); 31P{1H} NMR
(242 MHz, [D6]benzene, 258C): d=64.3 (dd, 1J(P,Pt)=2123 Hz,
13C{1H} NMR (151 MHz, [D6]benzene, 258C): d=165.7 (brs; C2),
151.4 (brs; ipso-BPh), 147.4 (d, 1J(C,P)=46 Hz; C1), 145.9 (d,
1
3J(C,P)=3 Hz; ipso-Pha), 142.7 (s; ipso-Phb), 138.6 (d, J(C,P)=44 Hz;
2J(P,H)=19 Hz, J(P,P)=10 Hz; C5H4P(tBu)Ar), 24.1 ppm (d, J(Pt,P)=
3721 Hz, 2J(P,P) 10 Hz; C5H4PPh2); 11B NMR (161 MHz, [D6]benzene,
258C): d=6 ppm (brs, w1/2 =1200 Hz); 11B NMR (161 MHz,
[D2]methylene chloride, 258C): d=5 ppm(brs, w1/2 =1200 Hz);
195Pt{1H} NMR (128 MHz, [D2]methylene chloride, 258C): d=
À4980 ppm (dd, 1J(Pt,P)=3753 Hz, 1J(Pt,P)=2130 Hz); IR (CH2Cl2):
n˜ =2020 (PtÀH, br), 1822 cmÀ1 (Pt-H-B, v br). Elemental analysis
could not be obtained due to the instability of 4 under dynamic
vacuum.
2
1
2
ipso-PPh2 A), 135.6 (d, J(C,P)=15 Hz; o-PPh2 A), 134.6 (appt. d, J=
27 Hz; ipso-PPh2 B, C6), 134.2 (s; o-BPh), 132.7 (s; p-Pha), 131.5 (s; o-
2
Phb), 131.4 (d, J(C,P)=13 Hz; o-PPh2 B), 130.6 (s; p-PPh2 A, o-Pha),
129.7 (s; C5), 128.4 (s; o-Pha), 128.3 (d, 3J(C,P)=11 Hz; m-PPh2 A),
3
128.2 (s; p-PPh2 B), 127.6 (d, J(C,P)=10 Hz; m-PPh2 B), 127.3 (s; m-
BPh), 126.7 (s; m-Phb), 126.6 (s; m-Pha), 125.7 (s; p-BPh), 124.7 (d,
4J(C,P)=6 Hz; C4), 124.3 (s; p-Phb), 123.7 (s; C3), 114.0 (brs; vinylCa),
85.9 (d, 1J(C,P)=51 Hz; C1’’), 82.4 (d, 1J(C,P)=40 Hz; C1’), 77.7 (dd,
2
2
2J(C,P)=34 Hz, J(C,P)=4 Hz; vinylCb), 75.0 (d, J(C,P)=13 Hz; C2’/5’),
74.6 (d, 2J(C,P)=6 Hz; C5’/2’), 74.5 (s; C2’’/5’’), 73.7 (s; C5’’/2’’), 71.7 (d,
3J(C,P)=6 Hz; C3’/4’), 70.2 (d, J(C,P)=7 Hz; C3’’/4’’), 69.7 (s; C4’/3’), 69.2
(s; C4’’/3’’), 35.5 (d, J(C,P)=24 Hz; CMe3), 29.1 ppm (d, J(C,P)=5 Hz,
CMe3); 31P{1H} NMR (203 MHz, [D6]benzene, 258C): d=50.3 (d,
1J(P,Pt)=3695 Hz, 2J(P,P) 19 Hz; C5H4P(tBu)Ar), 27.6 ppm (d,
1J(Pt,P)=3937 Hz, 2J(P,P) 19 Hz; C5H4PPh2); 11B NMR (161 MHz,
[D6]benzene, 258C): d=24 ppm (brs, w1/2 =1200 Hz); 11B NMR
[PtD(m-D)(FcPPB)] ([D]-4): This compound was generated by the
same method as described for compound 4, but using D2 instead
of H2. IR (CH2Cl2): n˜ =1478 cmÀ1 (PtÀD, br). The Pt-D-B stretch was
not located due to broadness, combined with spectral overlap
[predicted 1428 cmÀ1 (PtÀD) and 1288 cmÀ1 (Pt-D-B) by Hooke’s
Law].
3
1
2
Spectroscopic data for [Pt(C2Ph)(m-H)(FcPPB)] (5): NMR data was
collected via in situ generation of compound 5; IR data was col-
lected following evaporation of the reaction solvent in vacuo, thus
isolating a sample that contained compounds 5 and 6A in an ap-
proximate 1:1 ratio. The IR data was collected in nujol. 1H NMR
(161 MHz, [D2]methylene chloride, 258C): d=24 ppm (brs, w1/2
=
1200 Hz); 195Pt{1H} NMR (128 MHz, [D2]methylene chloride, 258C):
1
d=À5117 ppm (dd, J(Pt,P)=3950 Hz, 1J(Pt,P)=3689 Hz).
NMR data for 6B: 1H NMR (500 MHz, [D6]benzene, 258C): d=7.88
(dq, 3J(H,P)=11 Hz, 3J(H,H)=8 Hz, 4J(H,H)=2 Hz, 2H; o-PPh2 A or
B), 7.84 (d, 3J(H,H)=7 Hz, 2H; o-BPh), 7.73–7.70 (m, 3H; o-Pha,
phenyl-CH), 7.28–7.21 (m, 4H; phenyl-CH), 7.14–6.96 (m, 11H;
phenyl-CH), 6.85–6.84 (m, 5H; phenyl-CH), 6.81–6.75 (m, 2H;
3
3
(500 MHz, [D6]benzene, 258C): d=8.40 (q, J(H,P)=11 Hz, J(H,H)=
3
8 Hz, 2H; phenyl-CH), 7.80 (d, J(H,H)=7 Hz, 2H; phenyl-CH), 7.75
(d, 3J(H,H)=7 Hz, 1H; phenyl-CH), 7.53–7.49 (m, 3H; phenyl-CH),
7.34–7.30 (m, 5H; phenyl-CH), 7.01–6.96 (m, 6H; phenyl-CH), 6.85–
6.84 (m, 4H; phenyl-CH), 4.88 (s, 1H; C5H4), 4.33 (s, 1H; C5H4), 4.27
(s, 1H; C5H4), 3.96 (s, 1H; C5H4), 3.85 (s, 1H; C5H4), 3.76 (s, 1H;
2
3
3
phenyl-CH), 5.20 (dd, J(H,Pt)=55 Hz, J(H,P)=15 Hz, J(H,P)=5 Hz,
1H; vinylCb-H), 4.88 (s, 1H; C5H4), 4.41 (s, 1H; C5H4), 4.23 (s, 1H;
C5H4), 4.18 (s, 1H; C5H4), 3.95 (s, 1H; C5H4), 3.91 (s, 1H; C5H4), 3.84
(s, 1H; C5H4), 3.81 (s, 1H; C5H4), 1.01 ppm (d, 3J(H,P)=15 Hz, 9H;
CMe3); 13C{1H} NMR (151 MHz, [D6]benzene, 258C): d=162.9 (brs;
phenyl-C), 152.4 (brs; ipso-BPh), 147.5 (d, 1J(C,P)=47 Hz; ipso-
3
C5H4), 3.71 (s, 1H; C5H4), 3.55 (s, 1H; C5H4), 1.29 (d, J(H,P)=15 Hz,
9H; CMe3), À3.69 ppm (dd, 1J(H,Pt)=760 Hz, 2J(H,P)=115 Hz,
2J(H,P)=12 Hz, 1H; Pt-H-B); 31P{1H} NMR (203 MHz, [D6]benzene,
258C): d=62.9 (d, 1J(P,Pt)=2594 Hz, 2J(P,P) 12 Hz; C5H4P(tBu)Ar),
27.8 ppm (d, 1J(Pt,P)=3252 Hz, 2J(P,P) 12 Hz; C5H4PPh2); 11B NMR
(161 MHz, [D6]benzene, 258C): d=11 ppm (brs, w1/2 =1500 Hz); IR
(nujol): n˜ =2126 cmÀ1 (CꢀC).
1
phenyl-C), 145.6 (dd, J(C,P)=45 Hz, J(C,P)=9 Hz; phenyl-C), 144.1
(d, J(C,P)=6 Hz; phenyl-C), 143.8 (d, J(C,P)=4 Hz, phenyl-C), 138.6
1
(d, J(C,P)=42 Hz; ipso-phenyl-C), 137.2 (d, J(C,P)=17 Hz; o-PPh2 A
cis-[Pt(FcPPB’)] (6A/6B):
A
solution of [Pt(FcPPB)]·0.3 hexanes
or B), 135.8 (d, J(C,P)=24 Hz; phenyl-C), 135.6 (s; o-BPh), 134.0 (d,
(78.9 mg, 8.58ꢂ10À2 mmol) and PhC2H (9.0 mg, 8.81ꢂ10À2 mmol)
in benzene (10 mL) was allowed to stir for 6 days at room tempera-
ture. The reaction mixture was then evaporated to dryness in
vacuo to yield a yellow/brown oily residue. Hexanes (20 mL) were
added to the crude product and the resulting solution was sonicat-
ed for 15 min, after which point the resulting solution was evapo-
rated to dryness in vacuo to yield a beige solid, which consisted of
6A and 6B in a 45:55 ratio. Yield=65 mg (76%). Single crystals of
6A were obtained by dissolving a mixture of 6A and 6B in ben-
1J(C,P)=39 Hz; phenyl-C), 133.5 (d, J(C,Pt)=24 Hz, 4J(C,P)=4 Hz; o-
3
Pha), 133.1 (s, phenyl-C), 132.6 (d, J(C,P)=6 Hz; phenyl-C), 132.0 (d,
J(C,P)=13 Hz; phenyl-C), 131.2 (s; phenyl-C), 130.2 (s; phenyl-C),
129.2 (s; phenyl-C), 128.3 (s; phenyl-C), 128.0 (d, J(C,P)=10 Hz;
phenyl-C), 127.4 (s; phenyl-C), 127.1 (s; phenyl-C), 126.8 (s; phenyl-
C), 125.4 (s; phenyl-C), 125.2 (d, J(C,P)=6 Hz; phenyl-C), 124.4 (s;
1
3
phenyl-C), 93.8 (brs; vinylCa), 89.5 (dd, J(C,P)=51 Hz, J(C,P)=4 Hz,
C1’’), 85 5 (d, J(C,P)=36 Hz; C1’), 75.7 (d, J(C,P)=12 Hz; C5H4), 74.5
1
(d, J(C,P)=13 Hz; C5H4), 74.1 (d, J(C,P)=7 Hz; C5H4), 73.7 (d, J(C,P)=
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3 Hz; C5H4), 73.1 (d, J(C,P)=4 Hz; C5H4), 71.6 (dd, 2J(C,P)=37 Hz,
2J(C,P)=5 Hz; vinylCb), 71.3 (d, J(C,P)=7 Hz; C5H4), 69.9 (d, J(C,P)=
3 Hz; C5H4), 69.7 (s; C5H4), 69.2 (d, J(C,P)=4 Hz; C5H4), 35.2 (d,
1J(C,P)=66 Hz; CMe3), 30.3 ppm (d, 2J(C,P)=7 Hz, CMe3); 31P{1H}
NMR (203 MHz, [D6]benzene, 258C): d=55.7 (d, 1J(P,Pt)=3449 Hz,
2J(P,P) 20 Hz; C5H4P(tBu)Ar), 23.3 ppm (d, 1J(Pt,P)=4090 Hz, 2J(P,P)
20 Hz; C5H4PPh2); 11B NMR (161 MHz, [D6]benzene, 258C): d=
32 ppm (brs, w1/2 =1500 Hz); 11B NMR (161 MHz, [D2]methylene
chloride, 258C): d=30 ppm (brs, w1/2 =1500 Hz); 195Pt{1H} NMR
(128 MHz, [D2]methylene chloride, 258C): d=À4840 ppm (dd,
1J(Pt,P)=4097 Hz, 1J(Pt,P)=3440 Hz).
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the same method as described for compounds 6A/6B, but using
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that of a mixture of 6A/6B, but with the C6H5 resonances from the
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1
activated HC2Ph unit missing from the H NMR spectrum.
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Published online on && &&, 0000
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FULL PAPER
&
Boranes
B. E. Cowie, D. J. H. Emslie*
&& – &&
Platinum Complexes of a Borane-
Appended Analogue of 1,1’-
Bis(diphenylphosphino)ferrocene:
Flexible Borane Coordination Modes
and in situ Vinylborane Formation
Vinyl goes platinum! A borane-append-
ed analogue of 1,1’-bis(diphenylphos-
phino)ferrocene (FcPPB) was prepared,
and reaction with tris(norbornene)plati-
num provided [Pt(FcPPB)] in which the
arylborane is h3BCC-coordinated. Subse-
quent reactions of [Pt(FcPPB)] with CO,
CNXyl (Xyl=2,6-dimethylphenyl) and H2
afforded complexes featuring h2BC-,
h1B- and Pt-H-B coordination modes,
respectively. Further, reaction of PhC2H
with [Pt(FcPPB)] afforded [Pt(FcPPB’)] in
which the arylborane of FcPPB is
converted into an h3BCC-coordinated
vinylborane.
An arylborane-appended
analogue…
…of the catalytically important
dppf ligand, FcPPB, was prepared
and is represented by the industrial
robot in the image. FcPPB provided
access to platinum complexes
featuring h3BCC-, h2BC-, h1B- and Pt–
H–B coordination modes, and
reaction of the h3BCC-coordinated
complex with PhC2H transformed
the arylborane into an h3BCC-
coordinated vinylborane. For details,
see the Full Paper by B. E. Cowie
and D. J. H. Emslie on pp.&& ff.
Chem. Eur. J. 2014, 20, 1 – 15
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These are not the final page numbers! ÞÞ