Synthesis and characterization of Ni(II) and Pd(II) complexes bearing achiral and chiral bidentate aminophosphine ligands

Article abstract of DOI:10.1135/cccc20070527

The synthesis of a range of achiral and chiral bidentate aminophosphine ligands and their complexes with nickel(II) and palladium(II) has been investigated. The ligands and the complexes have been characterized by NMR spectroscopy, and X-ray structures of representative compounds have been determined. In addition, DFT calculations have been performed to investigate different geometries of the nickel(II) complexes in the solid state and in solution.

Full text of DOI:10.1135/cccc20070527

Bidentate Aminophosphine Ligands
527
SYNTHESIS AND CHARACTERIZATION OF Ni(II) AND Pd (II)
COMPLEXES BEARING ACHIRAL AND CHIRAL BIDENTATE
AMINOPHOSPHINE LIGANDS
b
a2,
David BENITO-GARAGORRIa1, Kurt MEREITER and Karl KIRCHNER
*
a
Institute of Applied Synthetic Chemistry, Vienna University of Technology,
1
Getreidemarkt 9, A-1060 Vienna, Austria; e-mail: garagorri@ioc.tuwien.ac.at,
2
kkirch@mail.zserv.tuwien.ac.at
b
Institute of Chemical Technologies and Analytics, Vienna University of Technology,
Getreidemarkt 9, A-1060 Vienna, Austria; e-mail: kmereite@mail.zserv.tuwien.ac.at
Received March 1, 2007
Accepted April 11, 2007
Dedicated to Dr Karel Mach on the occasion of his 70th birthday in recognition of his contributions to
the area of organometallic chemistry.
Th e syn th esis of a ran ge of ach iral an d ch iral biden tate am in oph osph in e ligan ds an d th eir
com plexes with n ickel(II) an d palladium (II) h as been in vestigated. Th e ligan ds an d th e com -
plexes h ave been ch aracterized by NMR spectroscopy, an d X-ray structures of represen tative
com poun ds h ave been determ in ed. In addition , DFT calculation s h ave been perform ed to
in vestigate differen t geom etries of th e n ickel(II) com plexes in th e solid state an d in solution .
Keyw ord s: Am in oph osph in es; Nickel; Palladium ; Allyl com plexes; DFT calculation s.
Th e coordin ation ch em istry of pyridylph osph in e ligan ds h as been exten -
sively studied1. Most research in th is area h as been focused on th e ch em is-
try of 2-(diph en ylph osph in o)pyridin e, wh ich can act as a biden tate ligan d
con tain in g both h ard (n itrogen ) an d soft (ph osph orus) don or atom s. How-
ever, ch elate com plexes with th is ligan d are un stable because of rin g strain ,
an d oth er ligan d system s con tain in g th e sam e don or groups with organ ic
spacers between th e ph osph orus an d th e pyridin e n itrogen atom h ave been
2
3
4
reported, in cludin g Ph 2PCH(R)py (R = H , CH2OEt , PPh 2
Ph 2PCH2CH2py 5.
) an d
Surprisin gly, con siderin g th e ease of ph osph in e–n itrogen bon d form in g
reaction s, th ere are on ly few exam ples of PN ligan ds in wh ich th e ph os-
ph in e an d th e pyridin e rin gs are separated by am in o groups6. We h ave re-
cen tly reported a n ew class of triden tate PNP an d PCP pin cer ligan ds in
wh ich an am in e acts as spacer between th e arom atic rin g an d th e ph os-
Collect. Czech. Chem. Commun. 2007, Vol. 72, No. 4, pp. 527–540
© 2007 Institute of Organic Chemistry and Biochemistry
doi:10.1135/cccc20070527

528
Benito-Garagorri, Mereiter, Kirchner:
ph in es7. In th ese ligan ds, th eir steric, electron ic an d stereoch em ical proper-
ties can be easily m odulated by usin g differen t ph osph in e substituen ts. In
th is article we apply th e sam e syn th etic m eth odology to th e preparation of
several biden tate PN ligan ds wh ich con tain aryl- an d alkylph osph in es as
well as differen t P–O bon d con tain in g ach iral an d ch iral ph osph in e un its.
Furth erm ore, th ese ligan ds h ave been applied to th e syn th esis of several
Ni(II) an d Pd(II) com plexes.
RESULTS AND DISCUSSION
Ligands
Sim ilarly to th e kn own ligan d 2-[(diph en ylph osph in o)am in o]pyridin e
(PN-Ph ; 1a)6e, th e n ew PN ligan ds 1b–1d were prepared in 88–95% yields by
treatm en t of 2-am in opyridin e with 1 equivalen t of th e respective ch loro-
ph osph in e or ch loroph osph ite in th e presen ce of a base (NEt3) (Sch em e 1).
Th e reaction s were carried out in toluen e at 80 °C for 3 h . Th e ligan ds
1
1a–1d were isolated as air-stable solids or oils an d were ch aracterized by H,
1
1
1
13C{ H} an d 31P{ H} NMR spectroscopics. Most diagn ostic are th e 31P{ H}
NMR spectra, wh ich exh ibit a sin gle reson an ce in th e ran ge between 27.5
1
(1a) an d 147.3 ppm (1c). In th e H NMR spectra, th e NH proton s of 1a–1d
give rise to a broaden ed sin glet between 4.94 an d 6.60 ppm . All oth er reso-
n an ces are un rem arkable an d are n ot discussed h ere.
SCHEME 1
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Bidentate Aminophosphine Ligands
529
Nickel(II) Complexes
Th e tetracoordin ated n ickel(II) com plexes [NiCl2(PN-Ph )] (2a) an d
[NiCl2(PN-iPr)] (2b) were prepared in 86 an d 92% yields, respectively, by re-
actin g equim olar am oun ts of [NiCl2(dm e)] an d of th e ligan ds 1a, 1b in
CH2Cl2 at room tem perature for 2 h (Sch em e 2). Com plexes 2a, 2b are para-
1
m agn etic an d give rise to very broad sign als in th e H NMR spectra in dicat-
in g a tetrah edral coordin ation geom etry aroun d th e m etal cen ter in
1
1
solution . No sign als could be observed in th e 13C{ H} an d 31P{ H} NMR
spectra. Th is observation is in agreem en t with th e fin din gs reported by
Braun stein et al.8 with sim ilar n ickel(II)-PN com plexes.
SCHEME 2
Th e solid-state structure of 2b was determ in ed by X-ray diffraction . A view
of th e m olecular structure is sh own in Fig. 1 with selected bon d len gth s an d
an gles given in th e caption . Th e n ickel(II) cen ter in 2b sh ows a sligh tly dis-
FIG. 1
Structure view of 2b sh owin g atom ic displacem en t ellipsoids drawn at 40% probability level.
C-bon ded h ydrogen atom s are om itted for clarity. Selected bon d len gth s (in Å) an d an gles (in °):
P–N2 1.6839(11), Ni–N1 1.9259(10), Ni–P 2.1209(4), Ni–Cl1 2.1710(4), Ni–Cl2 2.2359(3);
N1–Ni–P 86.55(3), N1–Ni–Cl2 95.74(3), P–Ni–Cl1 84.34(2), Cl1–Ni–Cl2 93.39(2)
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Benito-Garagorri, Mereiter, Kirchner:
torted square-plan ar geom etry. Th is result is surprisin g in view of th e para-
m agn etic n ature of th is com plex in solution , but of course solution an d
solid-state structures n eed n ot be iden tical9,10, an d such differen ces between
th e geom etry in solution an d in th e solid state h ave been reported previ-
ously for a sim ilar n ickel(II)-PN com plex8a. In agreem en t with th e experi-
m en tal results, DFT calculation s reveal th at th e tetrah edral geom etry is
favored over th e square-plan ar on e by about 40–60 kJ/m ol both in th e gas
ph ase an d in th e solution (CH2Cl2 an d aceton e). Th e two geom etries, i.e. A
tetrah edral (S = 1) an d B square-plan ar (S = 0), an d relative en ergies of th e
m odel com plexes [NiCl2(PN-Me)] an d [NiCl2(PN-Ph )] calculated at th e
B3LYP level of th eory are depicted in Fig. 2.
Th e Ni–Cl bon d distan ce is about 0.05 Å sh orter for th e ch lorin e in th e
trans position to th e pyridin e n itrogen atom (Ni–Cl1 2.1710(4) Å) th an th at
for th e ch lorin e trans to th e ph osph orus atom (Ni–Cl2 2.2359(3) Å). Th e
ligan d bite an gle (N1–Ni–P) is 86.55(3)°, wh ich is sligh tly bigger th an th at
observed in related ph osph in opyridin e8a an d ph osph in ooxazolin e11
n ickel(II)-PN com plexes. Th e r.m .s. deviation of th e four Ni ligan ds from
perfect plan arity is on ly 0.023 Å. A sign ifican t distortion from th e exact
quadratic geom etry is eviden t from th e bon d an gles at Ni (Fig. 1). Th e com -
paratively large bon d an gle N1–Ni–Cl2 = 95.74(3)° is caused by steric con -
gestion in volvin g th e h ydrogen of C1 an d its sh ort con tact to Cl2 (H···Cl =
2.49 Å) alth ough it represen ts a n on -classic h ydrogen bon d in teraction .
FIG. 2
Optim ized geom etries and relative energies (in kJ/m ol) for the m odel com plexes [NiCl2(PN-Me)]
an d [NiCl2(PN-Ph )] with tetrah edral (A) an d square-plan ar (B) geom etries calculated at th e
B3LYP level of th eory (Ni sdd; C, N, P, Cl, H 6-31g**)
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Bidentate Aminophosphine Ligands
531
Palladium(II) Complexes
Treatm en t of 1 equivalen t of [Pd(cod)Cl2] with 1 equivalen t of th e ligan ds
1a–1d in CH2Cl2 at room tem perature for 2 h afforded th e n eutral PN com -
plexes of th e gen eral form ula [PdCl2(PN)] (3a–3d ) clean ly in good isolated
yields (74–91%) (Sch em e 3). Th e com plexes 3a–3d are th erm ally robust
yellow solids th at are air-stable both in th e solid state an d in solution ; th eir
1
1
1
iden tity was establish ed by H, 13C{ H} an d 31P{ H} NMR spectroscopies. In
th e 31P{ H} NMR spectra, th e com plexes sh ow a sin gle reson an ce at 79.5
1
(3a), 125.7 (3b), 109.5 (3c) an d 118.5 ppm (3d ). All th e oth er reson an ces
are n ot rem arkable an d are n ot discussed h ere. It h as to be n oted th at pre-
vious reports about th e reaction of 1a with palladium m etal precursors in -
dicate th at wh en th e reaction is carried out in th e [PdCl2(cod)]:1a m olar
ratio 1:2 in refluxin g aceton e, th e cation ic species cis-[PdCl(Ph -PN-P,N)-
(Ph -PN-P)]Cl is obtain ed, with n o eviden ce for th e form ation of trans
bis(PN) or m on o(PN) dich loro-Pd(II) com plexes6e.
SCHEME 3
Given th e im portan ce of tran sition m etal allyl com plexes in catalytic re-
action s, wh ere th ey often represen t key in term ediates12, we were in terested
in preparin g both η1- an d η3-allyl palladium (II) com plexes with th e PN
ligan ds described above. Fully ch aracterized η1- an d η3-allyl palladium (II)
com plexes h ave been previously reported13. Th us, th e reaction of th e
dim eric precursor [Pd(η3-allyl)Cl]2 with 2 equivalen ts of th e ligan ds 1a, 1b
in CH2Cl2 at room tem perature for 2 h afforded, upon workup, th e Pd(II)
η1-allyl com plexes 4a, 4b as air-stable yellow solids in m oderate to good
yields (68–83%) (Sch em e 4). Altern atively, treatm en t of 1 equivalen t of
[Pd(η3-allyl)Cl]2 with 2 equivalen ts of AgBF4 in aceton itrile yields th e in ter-
m ediate [Pd(η3-allyl)(CH3CN)2]BF4, wh ich on addition of 2 equivalen ts of
th e ligan ds 1a, 1b gives th e Pd(II) η3-allyl com plexes 5a, 5b as air-stable
off-wh ite solids in good yields (75–92%) (Sch em e 4). Th e –CH= h ydrogen
atom in th e com plexes 4a, 4b an d 5a, 5b gives rise to m ultiplets between
5.66 (4b) an d 5.90 ppm (4a an d 5a), wh ile th e sign als of th e oth er allylic
proton s appear as doublets or m ultiplets between 3.19 an d 4.67 ppm in th e
1
case of 4a, 4b an d between 2.69 an d 6.81 ppm for 5a, 5b. In th e 13C{ H}
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532
Benito-Garagorri, Mereiter, Kirchner:
NMR spectra of 4a, 4b an d 5a, 5b, th e –CH=, =CH2 an d –CH2 carbon atom s
appear at about 120, 80 an d 45 ppm , respectively. All com plexes sh ow a
1
sin gle reson an ce in th e 31P{ H} NMR spectrum at 78.4 (4a), 115.3 (4b), 77.6
(5a) an d 115.4 ppm (5b).
SCHEME 4
Th e solid-state structures of 5a an d 5b were determ in ed by X-ray crystal-
lograph y. Structure views of 5a an d 5b are sh own in Figs 3 an d 4 with se-
lected bon d len gth s an d an gles given in th e caption s. Th e m etal cen ter in
com plexes 5a an d 5b adopts a distorted square-plan ar geom etry defin ed by
FIG. 3
Structure view of 5a sh owin g atom ic displacem en t ellipsoids drawn at 50% probability level.
C-bon ded h ydrogen atom s are om itted for clarity. Selected bon d len gth s (in Å) an d an gles (in °):
Pd–N1 2.0876(14), Pd–P 2.2499(4), P–N2 1.6953(13), Pd–C18 2.199(2), Pd–C19 2.160(2),
Pd–C20 2.112(2); N1–Pd–C20 173.34(7), P–Pd–C18 170.89(5), N1–Pd–C19 137.5(2),
C18–C19–C20 124.4(2); N2···F1 2.884(2)
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Bidentate Aminophosphine Ligands
533
th e palladium , ph osph orus an d pyridin e n itrogen atom s an d by th e two
lateral carbon atom s of th e allyl group. Th e r.m .s. deviation s of th ese four
ligan d atom s are 0.003 (5a) an d 0.021 Å (5b). Palladium an d th e cen tral
allyl carbon deviate distin ctly from th is plan e, in th e case of 5a by 0.038
an d 0.556 Å, in th e case of 5b by 0.078 an d 0.605 Å. Th e about 0.1 Å lon ger
Pd–C18 an d Pd–C14 bon ds in com plexes 5a an d 5b com pared to Pd–C20
an d Pd–C12, respectively, reflect th e larger trans in fluen ce of th e ph osph o-
rus don or, an d h ave been observed also in oxazolin e-based palladium -allyl
com plexes14. Th e ligan d bite an gle N1–Pd–P h as a value of 83.61(3) an d
83.40(6)° for 5a an d 5b, respectively.
FIG. 4
Structure view of 5b sh owin g atom ic displacem en t ellipsoids drawn at 50% probability level.
–
BF4 an ion an d C-bon ded h ydrogen atom s are om itted for clarity. Selected bon d len gth s (in Å)
an d an gles (in °): Pd–N1 2.110(2), Pd–P 2.2577(6), P–N2 1.694(2), Pd–C12 2.109(2), Pd–C13
2.168(3), Pd–C14 2.222(3); N1–Pd–C12 174.1(1), P1–Pd–C14 168.7(1), N1–Pd–C13 137.4(1),
C12–C13–C14 121.57
EXPERIMENTAL
Gen eral
All m an ipulation s were perform ed un der in ert atm osph ere of argon by usin g Sch len k tech -
n iques. Th e solven ts were purified accordin g to stan dard procedures. Th e startin g m aterials
PPh 2Cl an d PiPr2Cl were purch ased from Aldrich an d used with out furth er purification .
Biph en yl-2,2′-diyl ph osph oroch loridite15
,
dim eth yl (4S,5S)-2-ch loro-1,3,2-dioxaph os-
ph olan e-4,5-dicarboxylate16, [PdCl2(cod)] (cod = 1,5-cyclooctadien e)17, [Pd(η3-allyl)Cl]2 an d
[NiCl2(dm e)] (dm e = 1,2-dim eth oxyeth an e)18 were prepared accordin g to th e literature. Th e
deuterated solven ts were purch ased from Aldrich an d dried over 4 Å m olecular sieves. 1H,
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534
Benito-Garagorri, Mereiter, Kirchner:
1
1
13C{ H} an d 31P{ H} NMR spectra were obtain ed at room tem perature (20 °C) on a Bruker
AVANCE-250 spectrom eter. Ch em ical sh ift data (δ, ppm ) are referen ced to SiMe4 an d H3PO4
1
(85%), respectively. Couplin g con stan ts, J, are given in Hz. 1H an d 13C{ H} NMR sign al as-
sign m en ts were con firm ed by 1H-COSY, 135-DEPT an d HMQC(1H-13C) experim en ts.
Syn th eses
2-[(N-Diphenylphosphino)amino]pyridine (PN-Ph) (1a). PPh 2Cl (9.5 m l, 53.1 m m ol) was
added dropwise to a solution of 2-am in opyridin e (5.0 g, 53.1 m m ol) an d trieth ylam in e
(7.4 m l, 53.1 m m ol) in toluen e (50 m l) at 0 °C. Th e m ixture was stirred at 80 °C for 3 h , fil-
tered an d th e solven t was rem oved un der vacuum to give 1a as a pale yellow solid. Yield
12.9 g (87%). 1H NMR (CDCl3): 7.93 (d, J = 4.6, 1 H, 6-Hpy); 7.51–7.42 (m , 5 H, Ph );
7.36–7.33 (m , 6 H, Ph an d 4-Hpy); 7.06 (d, J = 8.2, 1 H, 3-Hpy); 6.64 (dd, J = 5.2, 6.4, 1 H,
1
5-Hpy); 5.93 (d, J = 8.4, 1 H, NH). 13C{ H} NMR (CDCl3): 158.7 (d, J = 20.7, 2-Hpy); 148.1
(d, J = 1.5, 6-Hpy); 139.6 (d, J = 11.1, Ph 1); 137.82 (d, J = 2.3, 4-Hpy); 131.3 (d, J = 20.7,
1
Ph 2,6); 129.2 (Ph 4); 128.6 (d, J = 6.9, Ph 3,5); 115.0 (5-Hpy); 108.9 (d, J = 15.7, 3-Hpy). 31P{ H}
NMR (CDCl3): 27.5.
2-[(N-Diisopropylphosphino)amino]pyridine (PN-iPr) (1b). Th is ligan d h as been prepared an al-
ogously to 1a with PiPr2Cl (8.5 m l, 53.1 m m ol), trieth ylam in e (7.4 m l, 53.1 m m ol) an d
2-am in opyridin e (5.0 g, 53.1 m m ol) as th e startin g m aterials. Yield 10.6 g (95%). 1H NMR
(CDCl3): 8.00 (d, J = 3.9, 1 H, 6-Hpy); 7.42 (dt, J = 1.5, 2.0, 1 H, 4-Hpy); 7.08 (s, 1 H, 3-Hpy);
6.61 (m , 1 H, 5-Hpy); 4.94 (d, J = 10.5, 1 H, NH); 1.77 (m , J = 2.3, 7.0, 2 H, CH(CH3)2);
1
1.09–0.99 (m , 12 H, CH(CH3)2). 13C{ H} NMR (CDCl3): 160.7 (d, J = 19.6, 2-Hpy); 147.5 (d,
J = 1.2, 6-Hpy); 137.6 (d, J = 2.0, 4-Hpy); 114.1 (5-Hpy); 108.9 (d, J = 18.0, 3-Hpy); 26.3 (d,
1
J = 11.1, CH(CH3)2); 18.6 (d, J = 19.5, CH(CH3)2); 17.0 (d, J = 7.7, CH(CH3)2). 31P{ H} NMR
(CDCl3): 50.1.
2-[(2-Pyridyl)amino]dibenzo[d,f][1,3,2]dioxaphosphepine (PN-BIPOL) (1c). Th is ligan d h as been
prepared an alogously to 1a with biph en yl-2,2′-diyl ph osph oroch loridite (1.1 g, 4.3 m m ol),
trieth ylam in e (0.60 m l, 4.3 m m ol) an d 2-am in opyridin e (405 m g, 4.3 m m ol) as th e startin g
m aterials. Yield 1.2 g (92%). 1H NMR (CDCl3): 8.12 (d, J = 5.0, 1 H, 6-Hpy); 7.54–7.47 (m , 3 H,
Ph an d 4-Hpy); 7.39–7.24 (m , 6 H, Ph ); 6.84–6.79 (m , 2 H, 3-Hpy an d 5-Hpy); 6.38 (s, 1 H,
1
NH). 13C{ H} NMR (CDCl3): 155.4 (d, J = 16.9, 2-Hpy); 149.6 (d, J = 4.2, Ph ); 148.3 (6-Hpy);
138.0 (d, J = 1.6, 4-Hpy); 131.6 (d, J = 3.1, Ph ); 129.8 (d, J = 1.1, Ph ); 129.2 (Ph ); 125.3 (Ph );
1
122.2 (d, J = 1.5, Ph ); 116.6 (5-Hpy); 110.2 (d, J = 11.1, 3-Hpy). 31P{ H} NMR (CDCl3): 147.3.
Dimethyl (4S,5S)-2-[(2-pyridyl)amino]-1,3,2-dioxaphospholane-4,5-dicarboxylate (PN-TARMe
)
(1d ). Th is ligan d h as been prepared an alogously to 1a with dim eth yl (4S,5S)-2-ch loro-1,3,2-
dioxaph osph olan e-4,5-dicarboxylate (1.5 g, 6.1 m m ol), trieth ylam in e (0.85 m l, 6.1 m m ol)
an d 2-am in opyridin e (577 m g, 6.1 m m ol) as th e startin g m aterials. Yield 1.6 g (88%). 1H NMR
(CDCl3): 8.14 (d, J = 5.0, 1 H, 6-Hpy); 7.48 (m , 1 H, 4-Hpy); 6.80 (m , 1 H, 3-Hpy); 6.70 (d,
J = 8.2, 5-Hpy); 6.60 (s, 1 H, NH); 5.10 (dd, J = 1.6, 5.2, 1 H, CH); 4.84 (dd, J = 5.2, 10.0,
1
1 H, CH); 3.83 (s, 3 H, CH3); 3.81 (s, 3 H, CH3). 13C{ H} NMR (CDCl3): 171.4 (CO); 169.2
(CO); 155.7 (d, J = 20.0, 2-Hpy); 148.0 (6-Hpy); 140.0 (4-Hpy); 116.6 (5-Hpy); 110.3 (d, J =
1
6.9, 3-Hpy); 77.2 (CH); 77.0 (CH); 53.2 (CH3); 53.1 (CH3). 31P{ H} NMR (CDCl3): 142.6.
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Bidentate Aminophosphine Ligands
535
[NiCl2(PN-Ph )] (2a)
1a (91 m g, 0.32 m m ol) was added to a suspen sion of [NiCl2(dm e)] (100 m g, 0.32 m m ol) in
CH2Cl2 an d th e m ixture was stirred at room tem perature for 2 h Th e solven t was evaporated
un der vacuum an d th e rem ain in g violet solid was wash ed twice with Et2O an d dried. Yield
108 m g (83%). For C17H15Cl2N2NiP (407.9) calculated: 50.06% C, 3.71% H, 6.87% N; foun d:
50.04% C, 3.77% H, 6.95% N.
[NiCl2(PN-iPr)] (2b)
Th is com plex h as been prepared an alogously to 2a with 1b (390 m g, 1.85 m m ol) an d
[NiCl2(dm e)] (405 m g, 1.85 m m ol) as th e startin g m aterials. Yield 490 m g (78%). For
C
11H19Cl2N2NiP (339.9) calculated: 38.87% C, 5.63% H, 8.24% N; foun d: 38.94% C, 5.57% H,
8.25% N.
[PdCl2(PN-Ph )] (3a)
1a (300 m g, 1.1 m m ol) was added to a solution of [PdCl2(cod)] (307 m g, 1.1 m m ol) in 20 m l
CH2Cl2 an d th e m ixture was stirred at room tem perature for 2 h . Th e solven t was th en re-
m oved un der vacuum an d th e rem ain in g yellow solid was wash ed twice with Et2O an d
dried. Yield 420 m g (88%). For C17H15Cl2N2PPd (455.6) calculated: 44.82% C, 3.32% H,
6.15% N; foun d: 44.92% C, 3.27% H, 6.15% N. 1H NMR (CD2Cl2): 10.11 (s, 1 H, NH); 9.00
(d, J = 5.8, 6-Hpy); 7.90–7.83 (m , 5 H, Ph ); 7.71–7.61 (m , 6 H, Ph an d 4-Hpy); 7.13 (d, J =
1
8.2, 3-Hpy); 7.03 (t, J = 6.5, 5-Hpy). 13C{ H} NMR (CD2Cl2): 161.8 (d, J = 10.7, 2-Hpy); 148.9
(6-Hpy); 142.1 (4-Hpy); 133.4 (d, J = 2.7, Ph ); 132.9 (d, J = 12.3, Ph 2,6); 129.6 (d, J = 12.3,
1
Ph 3,5); 128.8 (Ph 4); 116.7 (5-Hpy); 111.7 (d, J = 11.5, 3-Hpy). 31P{ H} NMR (CD2Cl2): 79.5.
[PdCl2(PN-iPr)] (3b)
Th is com plex h as been prepared an alogously to 3a with [PdCl2(cod)] (460 m g, 1.6 m m ol) an d
1b (340 m g, 1.6 m m ol) as th e startin g m aterials. Yield 565 m g (91%). For C11H19Cl2N2PPd
(387.6) calculated: 34.09% C, 4.94% H, 7.23% N; foun d: 34.00% C, 4.88% H, 7.25% N.
1H NMR (CD2Cl2): 8.90 (s, 1 H, NH); 8.83 (d, J = 5.2, 1 H, 6-Hpy); 7.84 (t, J = 7.8, 1 H,
4-Hpy); 7.07 (d, J = 8.2, 1 H, 3-Hpy); 6.95 (t, J = 6.4, 1 H, 5-Hpy); 2.47 (m , J = 7.1, 2 H,
CH(CH3)2); 1.38–1.20 (m , 12 H, CH(CH3)2). 13C{1H} NMR (CD2Cl2): 163.1 (d, J = 7.3,
2-Hpy); 148.5 (6-Hpy); 141.8 (4-Hpy); 116.3 (5-Hpy); 111.1 (d, J = 9.2, 3-Hpy); 28.1 (d, J =
1
32.2, CH(CH3)2); 17.8 (d, J = 2.0, CH(CH3)2); 16.8 (d, J = 2.5, CH(CH3)2). 31P{ H} NMR
(CD2Cl2): 125.7.
[PdCl2(PN-BIPOL)] (3c)
Th is com plex h as been prepared an alogously to 3a with [PdCl2(cod)] (92 m g, 0.32 m m ol) an d
1c (100 m g, 0.32 m m ol) as th e startin g m aterials. Yield 112 m g (74%). For C17H13Cl2N2O2PPd
(485.6) calculated: 42.05% C, 2.70% H, 5.77% N; foun d: 42.14% C, 2.67% H, 2.81% N.
1H NMR (CD2Cl2): 9.00 (d, J = 5.9, 1 H, 6-Hpy); 7.70 (t, J = 7.8, 1 H, 4-Hpy); 7.50–7.32 (m ,
8 H, Ph ); 7.17 (d, J = 7.3, 1 H, 3-Hpy); 6.94 (t, J = 7.3, 1 H, 5-Hpy); 6.25 (s, 1 H, NH).
1
13C{ H} NMR (CD2Cl2): 155.6 (d, J = 22.2, 2-Hpy); 149.3 (Ph ); 148.2 (d, J = 12.6, 6-Hpy);
141.5 (4-Hpy); 130.2 (Ph ); 128.9 (Ph ); 127.2 (Ph ); 122.5 (d, J = 4.2, Ph ); 117.9 (Ph ); 117.1
1
(5-Hpy); 111.6 (d, J = 12.6, 3-Hpy). 31P{ H} NMR (CD2Cl2): 109.5.
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Benito-Garagorri, Mereiter, Kirchner:
[PdCl2(PN-TARMe)] (3d )
Th is com plex h as been prepared an alogously to 3a with [PdCl2(cod)] (95 m g, 0.33 m m ol) an d
1d (100 m g, 0.33 m m ol) as th e startin g m aterials. Yield 118 m g (75%). For C11H13Cl2N2O6PPd
(477.5) calculated: 27.67% C, 2.74% H, 5.87% N; foun d: 27.64% C, 2.77% H, 5.75% N.
1H NMR (CD2Cl2): 9.17 (d, J = 6.2, 1 H, 6-Hpy); 7.33 (d, J = 8.2, 4-Hpy); 7.06 (t, J = 6.5, 1 H,
3-Hpy); 6.78 (t, J = 6.5, 1 H, 5-Hpy); 6.27 (s, 1 H, NH); 5.58 (dd, J = 4.3, 14.0, 1 H, CH); 5.41
1
(dd, J = 4.3, 13.9, 1 H, CH); 3.92 (s, 3 H, CH3); 3.86 (s, 3 H, CH3). 13C{ H} NMR (CDCl3):
168.0 (CO); 166.1 (CO); 149.5 (2-Hpy); 143.8 (6-Hpy); 142.0 (4-Hpy); 117.1 (5-Hpy); 111.7
1
(d, J = 14.6, 3-Hpy); 77.7 (d, J = 5, CH); 76.7 (d, J = 7.3, CH); 54.0 (CH3); 53.8 (CH3). 31P{ H}
NMR (CDCl3): 118.5.
[Pd(η1-allyl)Cl(PN-Ph )] (4a)
1a (160 m g, 0.58 m m ol) was added to a solution of [Pd(η3-allyl)Cl]2 (100 m g, 0.28 m m ol) in
15 m l CH2Cl2 an d th e m ixture was stirred at room tem perature for 2 h . Th e solven t was re-
m oved un der vacuum an d th e rem ain in g yellow solid was wash ed twice with Et2O an d
dried. Yield 217 m g (83%). For C20H20ClN2PPd (461.2) calculated: 52.08% C, 4.37% H,
6.07% N; foun d: 52.14% C, 4.47% H, 6.15% N. 1H NMR (CD2Cl2): 11.21 (s, 1 H, NH); 8.37
(d, J = 4.8, 6-Hpy); 7.90–7.74 (m , 6 H, Ph , 3-Hpy an d 4-Hpy); 7.49–7.26 (m , 6 H, Ph ); 6.69 (t,
J = 5.8, 5-Hpy); 5.90 (m , J = 10.6, CH); 4.67 (bs, 1 H, =CH); 4.06 (bs, 1 H, =CH); 3.32 (bs,
1
2 H, CH2). 13C{ H} NMR (CDCl3): 159.4 (d, J = 13.1, 2-Hpy); 149.6 (s, 6-Hpy); 137.8 (4-Hpy);
129.9 (d, J = 15.5, Ph 2,6); 129.4 (d, J = 2.5, Ph 4); 129.1 (Ph 1); 126.7 (d, J = 12.0, Ph 3,5); 122.8
(CH); 113.7 (5-Hpy); 111.8 (d, J = 8.1, 3-Hpy); 82.8 (=CH2); 45.2 (CH2). 31P{1H} NMR
(CDCl3): 78.4
[Pd(η1-allyl)Cl(PN-iPr)] (4b)
Th is com plex h as been prepared an alogously to 4a with 1b (121 m g, 0.58 m m ol) an d
[Pd(η3-allyl)Cl]2 (100 m g, 0.28 m m ol) as th e startin g m aterials. Yield 155 m g (68%). For
C
14H24ClN2PPd (393.2) calculated: 42.77% C, 6.15% H, 7.12% N; foun d: 42.74% C, 6.22% H,
7.15% N. 1H NMR (CD2Cl2): 10.40 (s, 1 H, NH); 8.23 (bs, 1 H, 6-Hpy); 7.81 (bs, 1 H, 4-Hpy);
7.56 (bs, 1 H, 3-Hpy); 6.65 (bs, 1 H, 5-Hpy); 5.66 (s, 1 H, CH); 4.66 (s, 1 H, =CH); 3.96 (s, 1 H,
=CH); 3.19 (s, 2 H, CH2); 2.56 (s, 2 H, CH(CH3)2); 1.20 (s, 12 H, CH(CH3)2). 13C{ H} NMR
1
(CDCl3): 163.4 (d, J = 10.0, 2-Hpy); 152.5 (6-Hpy); 140.1 (4-Hpy); 121.5 (d, J = 5.5, CH);
115.5 (5-Hpy); 113.9 (d, J = 7.5, 3-Hpy); 82.0 (d, J = 29.0, =CH2); 44.1 (CH2); 27.5 (d, J =
1
27.4, CH(CH3)2); 18.1 (CH(CH3)2). 31P{ H} NMR (CDCl3): 115.3.
[Pd(η3-allyl)(PN-Ph )](BF4) (5a)
AgBF4 (112 m g, 0.58 m m ol) was added to a solution of [Pd(η3-allyl)Cl]2 (100 m g, 0.28 m m ol)
in CH3CN (15 m l) an d th e m ixture was stirred at room tem perature in th e dark for 15 m in .
Th e solution was th en filtered un der argon , an d 1a (160 m g, 0.58 m m ol), dissolved in 5 m l
CH3CN, was added. Th e m ixture was stirred at room tem perature for furth er 30 m in , after
wh ich th e solven t was rem oved un der vacuum an d th e rem ain in g off-wh ite solid was
wash ed twice with Et2O an d dried. Yield 273 m g (92%). For C20H20BF4N2PPd (512.6) calcu-
lated: 46.87% C, 3.93% H, 5.47% N; foun d: 46.92% C, 3.93% H, 5.50% N. 1H NMR
(CD2Cl2): 8.34 (d, J = 5.3, 1 H, 6-Hpy); 8.24 (d, J = 4.2, 1 H, NH); 7.65–7.59 (m , 4 H, Ph ,
Collect. Czech. Chem. Commun. 2007, Vol. 72, No. 4, pp. 527–540

Bidentate Aminophosphine Ligands
537
3-Hpy an d 4-Hpy); 7.52–7.48 (m , 9 H, Ph an d 5-Hpy); 6.79 (t, J = 6.4, =CH); 5.90 (m , 1 H,
CH); 4.82 (t, J = 6.4, 1 H, =CH); 4.13 (d, J = 10.1, 1 H, CH2); 4.08 (d, J = 10.1, 1 H, CH2).
1
13C{ H} NMR (CDCl3): 159.0 (d, J = 13.4, 2-Hpy); 150.9 (6-Hpy); 139.4 (4-Hpy); 130.4 (d, J =
2.8, Ph 2,6); 130.1 (Ph 1); 129.8 (Ph 4); 127.5 (d, J = 12.4, Ph 3,5); 120.9 (d, J = 5.7, CH); 115.0
1
(5-Hpy); 111.9 (d, J = 7.4, 3-Hpy); 79.6 (d, J = 31.4, =CH2); 49.4 (CH2). 31P{ H} NMR (CDCl3):
77.6.
[Pd(η3-allyl)(PN-iPr)](BF4) (5b)
Th is com plex h as been prepared an alogously to 5a with AgBF4 (112 m g, 0.58 m m ol),
[Pd(η3-allyl)Cl]2 (100 m g, 0.28 m m ol) an d 1b (121 m g, 0.57 m m ol) as th e startin g m aterials.
Yield 93 m g (75%). For C14H24BF4N2PPd (444.5) calculated: 37.83% C, 5.44% H, 6.30% N;
foun d: 37.90% C, 5.51% H, 6.28% N. 1H NMR (CD2Cl2): 8.30 (d, J = 4.6, 1 H, NH); 7.63 (d,
J = 7.0, 1 H, 6-Hpy); 7.39–7.37 (m , 2 H, 3-Hpy an d 4-Hpy); 6.76 (t, J = 5.3, 5-Hpy); 5.70 (m ,
J = 6.4, 1 H, CH); 4.76 (s, 1 H, =CH); 4.03–3.92 (m , 2 H, CH2); 2.69–2.42 (m , 3 H, =CH an d
CH(CH3)2); 1.22–1.14 (m , 12 H, CH(CH3)2). 13C{1H} NMR (CDCl3): 162.4 (d, J = 10.0,
2-Hpy); 153.0 (6-Hpy); 140.9 (4-Hpy); 121.5 (d, J = 5.5, CH); 116.3 (5-Hpy); 113.1 (d, J = 7.0,
3-Hpy); 82.2 (d, J = 29.4, =CH2); 45.6 (CH2); 27.6 (d, J = 25.9, CH(CH3)2); 27.2 (d, J = 25.9,
1
CH(CH3)2); 18.2 (d, J = 8.0, CH(CH3)2); 17.3 (d, J = 15.0, CH(CH3)2). 31P{ H} NMR (CDCl3):
115.4.
X-ray Crystallograph y
X-ray data for 2b (in th e form of a disordered solvate obtain ed from aceton e/dieth yl eth er),
5a an d 5b were collected on a Bruker Sm art APEX CCD area detector diffractom eter usin g
graph ite-m on och rom atized MoKα radiation (λ = 0.71073 Å) an d 0.3° ω-scan fram es. Correc-
tion s for absorption , λ/2 effects, an d crystal decay were applied19. After structure solution
20
with program SHELXS97 refin em en t on F2 was carried out with th e program SHELXL97
.
Non -h ydrogen atom s were refin ed an isotropically. All H atom s were placed in calculated po-
sition s an d th ereafter treated as ridin g. Th e disordered solven t in 2b was squeezed with pro-
21
gram PLATON
an d it is n ot con tain ed in ch em ical form ula an d quan tities derived th ereof.
A m oderate orien tation disorder of th e allyl group in 5a was taken in to accoun t. Im portan t
crystallograph ic data for 2b: C11H19Cl2N2NiP, Mr = 339.86, red block, 0.35 × 0.32 × 0.20 m m ,
trigon al, space group R-3 (No. 148), a = 19.4562(6) Å, c = 21.4717(12) Å, V = 7039.0(5) Å3,
Z = 18, µ = 1.666 m m –1, T = 173 K. 32221 reflection s were collected up to θm ax = 30.0° an d,
after applyin g absorption correction s, m erged to 4559 in depen den t data (Rin t = 0.029),
fin al R in dices: R1 = 0.0267 (4066 reflection s with I > 2σ(I)), wR2 = 0.0715 (all data), 154 pa-
ram eters; for 5a: C20H20BF4N2PPd, Mr = 512.56, colorless prism , 0.45 × 0.25 × 0.24 m m ,
orth orh om bic, space group P212121 (No. 19), a = 9.9980(4) Å, b = 12.7834(5) Å, c =
15.9105(6) Å, V = 2033.50(14) Å3, Z = 4, µ = 1.036 m m –1, T = 100 K. 24216 reflection s were
collected up to θm ax = 30.06° an d, after applyin g absorption correction s, m erged to 5936 in -
depen den t data (Rin t = 0.019), fin al R in dices: R1 = 0.0168 (5852 reflection s with I > 2σ(I)),
wR2 = 0.0432 (all data), 266 param eters; for 5b: C14H24BF4N2PPd, Mr = 444.53, colorless
prism , 0.40 × 0.16 × 0.14 m m , orth orh om bic, space group P212121 (No. 19), a = 10.2776(6) Å,
b = 11.9892(7) Å, c = 15.1736(9) Å, V = 1869.7(2) Å3, Z = 4, µ = 1.112 m m –1, T = 100 K.
24084 reflection s were collected up to θm ax = 30.17° an d, after applyin g absorption correc-
tion s, m erged to 5516 in depen den t data (Rin t = 0.043), fin al R in dices: R1 = 0.0279 (5074 re-
flection s with I > 2σ(I)), wR2 = 0.0645 (all data), 208 param eters.
Collect. Czech. Chem. Commun. 2007, Vol. 72, No. 4, pp. 527–540

538
Benito-Garagorri, Mereiter, Kirchner:
Structure views of 2b, 5a an d 5b are sh own in Figs 1, 3 an d 4 with key bon d distan ces
an d an gles reported in th e caption s. All com plexes exh ibit N–H···X h ydrogen bon ds to adja-
cen t Cl or F atom s. CCDC 635593, 635594 an d 635595 (for 2b, 5a an d 5b) con tain th e
supplem en tary crystallograph ic data for th is paper. Th ese data can be obtain ed free of
ch arge via www.ccdc.cam .ac.uk/con ts/retrievin g.h tm l (or from th e Cam bridge Crystallo-
graph ic Data Cen tre, 12, Un ion Road, Cam bridge, CB2 1EZ, UK; fax: +44 1223 336033; or
deposit@ccdc.cam .ac.uk).
Com putation al Details
All calculation s were perform ed usin g th e Gaussian 03 software package on th e Silicon
Graph ics Origin 2000 of th e Vien n a Un iversity of Tech n ology22. Th e geom etry an d en ergy
of th e m odel com plexes an d th e tran sition states were optim ized at th e B3LYP level23 with
th e Stuttgart/Dresden ECP (SDD) basis set24 to describe th e electron s of th e n ickel atom . For
th e C, N, P, Cl an d H atom s th e 6-31g** basis set was em ployed25. Vibration al an alysis was
perform ed to con firm th at th e structures of th e m odel com poun ds h ave n o im agin ary fre-
quen cy. All geom etries were optim ized with out sym m etry con strain ts. Solvation effects were
evaluated with th e DPCM m eth od26
.
Financial support by the “Hochschuljubiläumsfonds der Stadt Wien” is gratefully acknowledged
(Project No. H-1024/2004). D. Benito-Garagorri thanks the Basque Government (Eusko Jaurlaritza/
Gobierno Vasco) for a doctoral fellowship.
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