Reactions of ruthenium-aminophosphane complexes with diynes: P-N bond activation and formation of novel phosphaallyl, azaallyl, and aminocarbene complexes

FULL PAPER

DOI: 10.1002/ejic.200500942

Reactions of Ruthenium–Aminophosphane Complexes with Diynes: P–N Bond

Activation and Formation of Novel Phosphaallyl, Azaallyl, and Aminocarbene

Complexes

Sonja Pavlik,^[a]Florian Jantscher,^[a]Georg Dazinger,^[a]Kurt Mereiter,^[b]and

Karl Kirchner*^[a]

Keywords: Ruthenium / Phosphaallyl complexes / Azaallyl complexes / Density functional calculations

The aminophosphane complexes [RuCp(PPh₂NRRЈ₂)-

(CH₃CN)₂]⁺and [RuCp*(PPh₂NRRЈ₂)(CH₃CN)₂]⁺(NRRЈ =

NHnPr, NEt₂, NC₅H₅) react with 1,6-heptadiyne and 1,7-oc-

The only exception is [RuCp*(PPh₂NHnPr)(CH₃CN)₂]⁺

where amido butadiene complexes [RuCp*{η¹-(N)-

NnPrPPh₂-η⁴-CH=C(CH₂)_nCH=CH₂}]PF₆(n = 3, 4) are ob-

tadiyne to yield novel η³-phosphaallyl–η²-vinylamine com- tained instead. In the case of [RuCp{η¹-(P)-PPh₂CH=C–(CH₂)₃–

plexes of the types [RuCp{η³-(P,C,C)-PPh₂CH=C–(CH₂)_n–η²-

(C,C)–C=CHNRRЈ₂}]⁺and [RuCp*{η³-(P,C,C)-PPh₂CH=C–

(CH₂)_n–η²-(C,C)-C=CHNRRЈ₂}]⁺(n = 3, 4). These complexes

are the kinetic products but eventually form the η¹-phos-

phaallyl–η³-azaallyl complexes [RuCp{η¹-(P)-PPh₂CH=C–

η³-(C,C,N)-CCHNRRЈ₂}]⁺with NRRЈ = NEt₂and NC₅H₅, a

further rearrangement took place at elevated temperatures

affording the aminocarbenes [RuCp{=C(NRRЈ)-η²-(C,C)-

C(CH₂)₃C–CH₂–(η¹-(P)-PPh₂)}]⁺. Representative X-ray struc-

tures are presented. Moreover, conceivable mechanisms for

all these reaction sequences are established by means of

DFT/B3LYP calculations.

(CH₂)_n–η³-(C,C,N)-CCHNRRЈ₂}]⁺

and

[RuCp*{η¹-(P)-

PPh₂CH=C–(CH₂)_n–η³-(C,C,N)-CCHNRRЈ₂}]⁺, respectively.

With n = 3 elevated temperatures are required, while with n

= 4 this conversion takes places already at room temperature.

Germany, 2006)

Introduction

Aminophosphanes that contain one or more direct

P^III–N bonds have received considerable attention in recent

years as ligands for transition metals.^[1]They are accessible

in large quantities through the use of relatively simple con-

densation processes from inexpensive starting materials,

that is, primary or secondary amines and PR₂Cl com-

pounds which contain dialkyl or diaryl substituents as well

as achiral and chiral P–O- and P–N-containing phosphane

units. Accordingly, variations of electronic, steric, and ste-

reochemical parameters may be achieved in a very facile

fashion. The most common structural types of such ligands

contain either one P–N unit (e.g. I),^[2]two or more P–N

units which are not directly bound (e.g. II),^[3,4]or a P–N–P

framework (e.g. III).^[5,6]It should be noted that in some

cases P^III–N bonds were found to be sensitive towards acid-

or base-catalyzed hydrolysis during complexation reac-

tions.^[7]However, by choosing appropriate substituents on

both phosphorus and nitrogen centers, P–N bond cleavage

can be avoided.

We have recently started to investigate the chemistry of

RuCp, RuCp*, and RuTp complexes that contain one or

two aminophosphane ligands of the most simple PR₂NHRЈ

type, I. In these compounds coordination takes place exclu-

sively through the phosphorus donor leaving the N-site

available for further reactions. We have shown, for instance,

that in the vinylidene and allenylidene complexes [RuCp-

(PPh₂NHR)₂{=C=(C)_n=CHRЈ}]⁺and [RuTp(PPh₂NHR)₂-

{=C=(C)_n=CHRЈ}]⁺(n = 0, 1; R = Ph, nPr; RЈ = alkyl,

aryl) an intramolecular addition of the NHRЈ moiety to the

α-carbon of the cumulene moiety takes place, resulting in

the formation of novel four-membered aza-phospha-carb-

enes.^[8]Complexes of the types [RuCp(PPh₂NHPh)-

(CH₃CN)₂]⁺and [RuCp*(PR₂NHRЈ)(CH₃CN)₂]⁺(R = Ph,

iPr, RЈ = Ph, C₆F₅) have been found to react with terminal

alkynes and diynes to give amido butadiene complexes.^[9,10]

In all these reactions, the N–H bond but not the P–N bond

is cleaved unless larger amounts of water are present. Re-

cently, when we switched over to a complex where the ami-

[a] Institute of Applied Synthetic Chemistry, Vienna University of

Technology,

Getreidemarkt 9, 1060 Vienna, Austria

Fax: +43-1-58801-15499

E-mail: kkirch@mail.zserv.tuwien.ac.at

[b] Institute of Chemical Technologies and Analytics, Vienna Uni-

versity of Technology,

Getreidemarkt 9, 1060 Vienna, Austria

nophosphane lacks

a

N–H bond viz. [RuCp-

1006

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Reactions of Ruthenium–Aminophosphane Complexes with Diynes

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(PPh₂NEt₂)(CH₃CN)₂]⁺, we discovered that it reacts with of the respective aminophosphane PPh₂NRRЈ (NRRЈ =

diynes to afford unusual and unprecedented phosphaallyl NHnPr, NEt₂, NC₅H₁₀) at room temperature. The analo-

complexes which readily rearrange to give azaallyl com- gous RuCp* complexes were obtained in a similar fashion

plexes.^[11]This process formally constitutes an insertion of by reacting [RuCp*(CH₃CN)₃]PF₆with PPh₂NRRЈ afford-

an unsaturated carbon C4 chain into the P–N bond, that ing complexes 2a–c. All these complexes are stable to air in

is, in the course of this reaction the P–N bond is cleaved. the solid state but decompose slowly in solutions on expo-

The present work is intended to investigate in detail the sure to air. Complexes 1a–c and 2a–c exhibit a singlet reso-

formation of phosphaallyl complexes and their conversion nance in the ³¹P{¹H} NMR spectrum in the range of 83–

to azaallyl complexes and we report here the reaction 102 ppm. Structural views of 1a and 2c are shown in Fig-

of

[RuCp(PPh₂NRRЈ)(CH₃CN)₂]PF₆

and

[RuCp*- ure 1 and Figure 2 with selected bond lengths given in the

(PPh₂NRRЈ)(CH₃CN)₂]PF₆(NRRЈ

=

NHnPr, NEt₂, captions.

NC₅H₁₀) with diynes. The mechanistic considerations will

be supported by DFT/B3LYP calculations.

Reaction of [RuCp(PPh₂NRRЈ)(CH₃CN)₂]⁺(NRRЈ =

NHnPr, NEt₂, NC₅H₁₀) with Diynes

Results and Discussion

Within a few minutes, treatment of 1a–c with 1,6-hep-

tadiyne results in the formation of the η³-phosphaallyl–η²-

vinylamine complexes [RuCp{η³-(P,C,C)-PPh₂CH=C–

Starting Materials

The starting complexes 1a–c were obtained in highly iso-

lated yields by reacting [RuCp(CH₃CN)₃]PF₆with 1 equiv.

(CH₂)₃-η²-(C,C)–C=CH–NHnPr}]⁺

(3a),

[RuCp{η³-

(P,C,C)-PPh₂CH=C–(CH₂)₃–η²-(C,C)-C=CH–NEt₂}]⁺

(3b), and [RuCp{η³-(P,C,C)-PPh₂CH=C–(CH₂)₃–η²-(C,C)-

C=CH–NC₅H₁₀}]⁺(3c) in high yields (Scheme 1).^[12,13]It

is interesting to note that despite the fact that the amino-

phosphane ligand of 1a bears a NH proton, a phospha-

allyl complex rather than an amido butadiene complex is

formed, as has been observed recently for [RuCp-

(Ph₂PNHPh)(CH₃CN)₂]⁺. This may be attributed to the

lower acidity of the NH proton (in other words, a stronger

N–H bond) in PPh₂NHnPr as compared to the NH bond

in PPh₂NHPh. Accordingly, P–N rather than N–H bond

activation is favored. The phosphaallyl composition proved

not to be the most stable one. In fact, if a solution of 3a–c

is kept at 90 °C for several hours, further rearrangement

takes place, leading eventually to the thermodynamically

more stable η¹-phosphaallyl–η³-azaallyl complexes [RuCp-

Figure 1. Structural view of [RuCp(PPh₂NHnPr)(CH₃CN)₂]PF₆

(1a) showing 50% thermal ellipsoids (PF₆^–omitted for clarity). Se- {η¹-(P)-PPh₂CH=C–(CH₂)₃–η³-(C,C,N)-C=CH–NHnPr}]⁺

lected bond lengths [Å]: Ru–C(1–5)_av2.187(2), Ru–N(2) 2.064(2),

(4a),

[RuCp{η¹-(P)-PPh₂CH=C–(CH₂)₃–η³-(C,C,N)-C=

Ru–N(3) 2.064(2), Ru–P(1) 2.2823(5), P(1)–N(1) 1.657(2).

CH–NEt₂}]⁺(4b), and [RuCp{η¹-(P)-PPh₂CH=C–(CH₂)₃–

η³-(C,C,N)-C=CH–NC₅H₁₀}]⁺(4c) in essentially quantita-

tive yields (Scheme 1).^[14]On the other hand, with 1a and

1,7-octadiyne no η³-phosphaallyl–η²-vinylamine complex

could be observed and the η¹-phosphaallyl–η³-azaallyl 4d

was obtained directly. In the case of 1b and 1c the respective

η³-phosphaallyl–η²-vinylamine complexes 3d and 3e could

be observed spectroscopically but rearranged rapidly at

room temperature to afford the corresponding η¹-phos-

phaallyl–η³-azaallyl complexes 4e and 4f. All compounds,

which are air-stable both in solution and in the solid state,

were fully characterized by ¹H, ¹³C{¹H}, and ³¹P{¹H}

NMR spectroscopy as well as elemental analysis.

1

The H NMR spectroscopic data for 3a include charac-

teristic resonances at 4.14 (d, J_HP= 4.4 Hz) and 3.99 ppm

(d, J_H,P= 7.6 Hz, 1 H) assignable to the protons H¹and

H⁴of the η³-phosphaallyl and η²-vinylamine units, respec-

tively. In the ¹³C{¹H} NMR spectrum the characteristic res-

onance of the coordinated sp²carbon atoms C¹, C², C³,

and C⁴of the η³-phosphaallyl–η²-vinylamine moiety exhi-

Figure 2. Structural view of [RuCp*(PPh₂NC₅H₁₀)(CH₃CN)₂]PF₆

(2c) showing 20% thermal ellipsoids (PF₆omitted for clarity). Se-

lected bond lengths [Å]: Ru–C(1–5)_av2.191(2), Ru–P(1) 2.3322(5),

Ru–N(2) 2.064(2), Ru–N(3) 2.059 (2), P(1)–N(1) 1.668(2).

–

Eur. J. Inorg. Chem. 2006, 1006–1021

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1007

S. Pavlik, F. Jantscher, G. Dazinger, K. Mereiter, K. Kirchner

FULL PAPER

Scheme 1.

bit resonances at 41.6 (d, J_CP= 24.5 Hz), 82.1, 116.8 (d, J_CPthe Ru–P, Ru–C(18), and Ru–C(19) bond lengths being

= 3.8 Hz), and 106.9 ppm (d, J_CP= 6.1 Hz), respectively. In 2.2763(5), 2.241(2), and 2.220(2) Å in 3a and 2.2505(4),

the ³¹P{¹H} NMR spectrum the phosphaallyl ligand exhib- 2.239(2), and 2.203(2) Å in 3c, respectively. The olefin part

its a singlet at 9.3 ppm. Concurrent NMR spectra are ob- of the vinylamine moiety is strongly asymmetrically bonded

served for 3b–e.

to the metal center with the Ru–C bonds to the carbon

The NMR spectroscopic data of 4a–f are quite different

from those of 3a–e. As the overall spectroscopic features

1

are very similar, we describe here only those of 4a. The H

NMR spectrum exhibits resonances at 5.98 (d, J_HP

=

10.1 Hz) and 6.02 ppm, which can be assigned to the ole-

finic hydrogen atom H¹and the allyl proton H⁴. The most

characteristic features in the ¹³C{¹H} NMR spectrum are a

low-field doublet resonance at δ = 170.1 ppm (d, J_CP

29.1 Hz) and doublet resonances at 111.9 (d, J_CP

=

47.2 Hz), 85.8 (d, J_CP= 1.9 Hz), and 74.4 ppm assignable

to the terminal allyl carbon atom C³, the two olefinic car-

bon atoms C¹and C², and the central allyl carbon atom C⁴

bearing the NHnPr unit. In the ³¹P{¹H} NMR spectrum

the η¹-(P)-phosphaallyl ligand exhibits a singlet at δ =

70.3 ppm (cf. 9.3 ppm in 3a).

The solid-state structures of 3a, 3c, and 4f were deter-

mined by single-crystal X-ray diffraction. ORTEP diagrams

are depicted in Figure 3, Figure 4, and Figure 5 with se-

lected bond lengths given in Table 1. The structures of 3a

and 3c can be described as a three-legged piano stool geom-

etry with the η³-phosphaallyl moiety and the C=C bond of

the vinylamine unit as the legs. The η³-phosphaallyl func-

Figure 3. Structural view of [RuCp{η³-(P,C,C)-PPh₂CHC–(CH₂)₃–

η²-(C,C)-CCHNHnPr}]PF₆(3a) showing 40% thermal ellipsoids

–

(PF₆omitted for clarity). Selected bond lengths [Å]: Ru–C(1–5)_av

2.197(2), Ru–P(1) 2.2763(5), Ru–C(18) 2.241(2), Ru–C(19)

2.220(2), Ru–C(23) 2.236(2), Ru–C(24) 2.490(2), P(1)–C(18)

1.768(2), C(18)–C(19) 1.4129(34), C(19)–C(23) 1.437(3), C(23)–

tionality is nearly symmetrically bonded to the metal with C(24) 1.396(3), C(24)–N 1.344(2).

1008 Eur. J. Inorg. Chem. 2006, 1006–1021

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Reactions of Ruthenium–Aminophosphane Complexes with Diynes

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atoms C(23) and C(24) being 2.236(2) and 2.490(2) Å in described as intermediate between the limiting vinylamine

3a and 2.219(2) and 2.551(2) Å in 3c, respectively. Strong and imine forms or alternatively perhaps even as η¹-(C)-

alteration of olefin binding by π-donor substituents has also azaallyl. Accordingly, rotation about the C(23)–C(24) bond

been observed in [FeCp(CO)₂(H₂C=CHNMe₂)]⁺where the is expected to be facile, putting the amine moiety rapidly

vinylamine is essentially η¹-bound [the nonbonded Fe···C in a syn-conformation for steric reasons (conversion D to

separation is 2.823(11) Å].^[15]In turn, the C(24)–N bonds complexes 3 in Scheme 1).

in 3a and 3c exhibit already double bond character being

1.344(2) and 1.359(2) Å, respectively. The bonding situation

of the –C=CHNHnPr and –C=CHNC₅H₁₀units might be

Figure 5. Structural view of [RuCp{η¹-(P)-PPh₂-CH=C(CH₂)₄-η³-

(C,C,N)-CH-NC₅H₁₀}]PF₆(4f) showing 40% thermal ellipsoids

–

(PF₆omitted for clarity). Selected bond lengths [Å]: Ru–C(1–5)_av

2.210(2), Ru–N 2.186(2), Ru–C(25) 2.089(2), Ru–C(24) 2.204(2),

Ru–P(1) 2.2791(5), P(1)–C(18) 1.796(2), C(18)–C(19) 1.336(2),

C(19)–C(24) 1.505(2), C(24)–C(25) 1.418(2), C(25)–N 1.415(2).

Figure 4. Structural view of [RuCp{η¹-(P)-PPh₂CH=C–(CH₂)₃–η³-

(C,C,N)-CCHNC₅H₁₀}]PF₆(3c) showing 40% thermal ellipsoids

–

(PF₆omitted for clarity). Selected bond lengths [Å]: Ru–C(1–5)_av

The structure of 4f also adopts a three-legged piano stool

conformation with the η³-azaallyl moiety and the P atom

as the legs. The η³-azaallyl unit, being exo-oriented with

respect to the phosphane moiety, is asymmetrically bonded

2.182(2), Ru–P(1) 2.2505(4), Ru–C(18) 2.239(2), Ru–C(19)

2.203(2), Ru–C(23) 2.219(2), Ru–C(24) 2.551(2), P(1)–C(18)

1.774(2), C(18)–C(19) 1.415(2), C(19)–C(23) 1.438(2), C(23)–C(24)

1.406(2), C(24)–N 1.359(2).

Table 1. Details for the crystal structure determinations of complexes 1a, 2c, 3a, 3c, 4f, and 5a.

1a 2c 3a 3c

Empirical formula C₂₄H₂₉F₆N₃P₂Ru C₃₁H₄₁F₆N₃P₂Ru C₂₇H₃₁F₆NP₂Ru C₂₉H₃₃F₆NP₂Ru C₃₀H₃₅F₆NP₂Ru C₂₈H₃₃F₆NP₂Ru

4f

686.60

5a

660.56

Formula mass

Crystalsize [mm]

Space group

a [Å]

b [Å]

c [Å]

636.51

732.68

646.54

672.57

0.46×0.34×0.22 0.62×0.48×0.33 0.62×0.37×0.07 0.62×0.24×0.09 0.52×0.29×0.14 0.47×0.36×0.21

P2₁/c (no. 14)

17.4288(10)

8.9607(5)

17.2306(10)

90

C2/c (no. 15)

21.7560(17)

18.7520(14)

18.6960(14)

90

P2₁/n (no. 14)

9.7404(5)

18.3098(9)

14.7423(8)

90

P2₁/n (no. 14)

17.6384(8)

8.8425(4)

18.9241(9)

90

P2₁/c (no. 14)

14.9183(7)

10.1274(5)

19.5913(9)

90

P2₁/n (no. 14)

8.9199(4)

15.6117(7)

20.3315(10)

90

α [°]

β [°]

93.502(1)

90

2686.0(3)

4

1.574

173(2)

120.954(1)

90

6541.1(9)

8

1.488

173(2)

0.637

90.134(1)

90

2629.2(2)

4

1.633

173(2)

0.779

108.100(1)

90

2805.5(2)

4

1.592

173(2)

0.733

91.835(1)

90

2958.4(2)

4

1.542

173(2)

0.697

93.219(1)

90

2826.8(2)

4

1.552

173(2)

0.726

γ [°]

V [Å³]

Z

ρ_calcd[g/cm³]

T [K]

µ [mm^–1] (Mo-K_α) 0.763

F(000)

θ_max[°]

1288

30

3008

30

1312

30

1368

30

1400

30

1344

27

Measured reflec-

tions

Unique reflections 7787

No. of reflections 6857

I Ͼ 2σ(I)

24957

48057

37914

40276

40996

25939

9522

8133

7615

6543

8167

6947

8570

7656

5719

5024

Parameters

345

416

343

375

367

343

R₁[I Ͼ 2σ(I)]^[a]

R₁(all data)

0.0337

0.0396

0.0838

–0.52/1.04

0.0343

0.0424

0.0949

–0.50/0.77

0.0292

0.0380

0.0823

–0.33/1.03

0.0282

0.0361

0.0732

–0.43/0.80

0.0316

0.0360

0.0881

–0.58/0.97

0.0899

0.0992

0.2279

–1.08/1.96

wR₂(all data)

∆ρ_min/max[e/Å³]

2 2

[a] R₁= Σ||F_o| – |F_c||/Σ|F_o|, wR₂= {Σ[w(F_o²–F_c) ]/Σ[w(F_o²)²]}^1/2

.

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S. Pavlik, F. Jantscher, G. Dazinger, K. Mereiter, K. Kirchner

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to the metal with the Ru–C bond length to the central allyl the range of 225.2 (d, J_CP= 13.0 Hz) and 222.9 (d, J_CP

=

carbon atom C(25) [2.089(2) Å] distinctly shorter than the 12.3 Hz) ppm, respectively, assignable to the carbene car-

Ru–N and Ru–C(24) bonds to the terminal allyl atoms N bon atoms. The sp³carbon atom C¹gives rise to a doublet

and C(24) [2.186(2) and 2.204(2) Å, respectively].

resonance at 37.9 (d, J_CP= 35.3 Hz) and 36.7 (d, J_CP=

Upon keeping a CH₃CN solution of 4b at 90 °C for 12 h, 35.3 Hz). The ³¹P{¹H} NMR spectrum reveals an unusually

an unexpected rearrangement took place affording the ami- high-field shifted resonance at –34.3 and –37.8 ppm (cf. 9.3

nocarbene [RuCp{=C(NEt₂)-η²-(C,C)-C(CH₂)₃CCH₂-(η¹- and 4.3 ppm in 3b and 3c, and 74.1 and 73.3 ppm in 4b and

(P)-PPh₂)}]⁺(5a) in essentially quantitative yield (71% iso- 4c) with a small coupling constant of 36 Hz. The structural

1

lated yield) as monitored by H and ³¹P{¹H} NMR spec- identity of 5a was unequivocally proven by X-ray crystal-

troscopy (Scheme 2). The same isomerization reaction was lography. The result is depicted in Figure 6 with important

observed for 4c yielding [RuCp{=C(NC₅H₁₀)-η²-(C,C)- bond lengths given in the caption. Overall, 5a adopts a typi-

C(CH₂)₃CCH₂-(η¹-(P)-PPh₂)}]⁺(5b) but the reaction was cal three-legged piano stool conformation with PPh₂, the

not quantitative. Attempts to isolate 5b in pure form were

unsuccessful and only mixtures of 4c and 5b were obtained.

All other azaallyl complexes turned out to be thermally

stable and there was no evidence for the formation of an

aminocarbene. In the course of this process, the hydrogen

of the central allyl carbon atom C⁴is transferred onto the

olefinic carbon C¹. It is interesting to note that this reaction

takes place only in the coordinating solvent CH₃CN, but

not in CH₃NO₂. It may be speculated that such a formal

1,4 hydrogen shift reaction proceeds most likely by a metal

mediated C–H activation step and the intermediacy of a

hydride species (Scheme 2). Addition of the coordinating

solvent may cause a hapticity change of the η³azaallyl moi-

ety to give a η²vinylamine, thereby providing a latent vac-

ant coordination site for a subsequent C–H bond activation

Figure 6. Structural view of [RuCp{=C(NEt₂)-η²-(C,C)-C(CH₂)₃-

C–CH₂-(η¹-(P)-PPh₂)}]PF₆(5a) showing 20% thermal ellipsoids

step. Insertion of the noncoordinated olefin moiety into the

Ru–H bond may then afford the aminocarbene complex.

The conversion of activated olefins to heteroatom-stabilized

carbenes is well documented.^[16]

–

(PF₆omitted for clarity). Selected bond lengths [Å]: Ru–C(1–5)_av

2.204(9), Ru–C(24) 2.006(7), Ru–C(23) 2.201(7), Ru–C(19)

2.444(8), Ru–P(1) 2.263(2), P(1)–C(18) 1.818(7), C(18)–C(19)

1.493(12), C(19)–C(23) 1.421(12), C(23)–C(24) 1.508(11), C(24)–N

Characteristic features of 5a and 5b comprise, in the

¹³C{¹H} NMR spectrum, a low-field doublet resonance in 1.147(9).

Scheme 2.

1010

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Reactions of Ruthenium–Aminophosphane Complexes with Diynes

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two C=C bonds of the vinyl moiety and the carbene carbon

atom as the legs. The most notable feature is the compara-

tively short Ru–C(24) bond length of 2.006(7) Å reflecting

metal carbon double bond character which is typical for

aminocarbenes. The η²-vinyl unit is asymmetrically bonded

to the metal center with Ru–C(23) and Ru–C(19) bond

lengths of 2.201(7) and 2.444(8) Å, respectively.

Reaction of [RuCp*(PPh₂NRRЈ)(CH₃CN)₂]⁺(NRRЈ =

NHnPr, NEt₂, NC₅H₅) with Diynes

Given the previously observed behavior differences be-

tween [CpRu(PR₃)(CH₃CN)₂]⁺and the homologous

[Cp*Ru(PR₃)(CH₃CN)₂]⁺complexes with respect to the C–

H activation processes,^[17]we have addressed the question

of whether P–N bond activation occurs also in the case

of the Cp* aminophosphane complexes 2a–c. In contrast

to 1a–c, the reaction of 2a both with 1,6-heptadiyne and

1,7-octadiyne results in the clean formation of the amido

Figure 7. Structural view of [RuCp*{η¹-(N)-NnPrPPh₂-η⁴-

CH=C(CH₂)₃CH=CH₂}]PF₆(6a) showing 40% thermal ellipsoids

–

(PF₆omitted for clarity). Selected bond lengths [Å]: Ru–C(1–5)_av

2.207(3), Ru–N = 2.183(2), Ru–C(26) 2.222(2), Ru–C(27) 2.232(2),

Ru–C(31) 2.227(2), Ru–C(32) 2.204(2), P(1)–N 1.600(2), P(1)–

C(26) 1.769(2), C(26)–C(27) 1.416(3), C(27)–C(31) 1.432(3), C(31)–

C(32) 1.401(3).

butadiene

complexes

[RuCp*{η¹-(N)-NnPrPPh₂-η⁴-

CH=C(CH₂)₃CH=CH₂}]PF₆(6a) and [RuCp*{η¹-(N)-

NnPrPPh₂-η⁴-CH=C(CH₂)₄CH=CH₂}]PF₆(6b) in high

yields (Scheme 3). There was no evidence that phosphaallyl

or azaallyl complexes were formed. The same reaction has

been found for [RuCp(PPh₂NHPh)(CH₃CN)₂]⁺and

[RuCp*(PR₂NHRЈ)(CH₃CN)₂]⁺(R = Ph, iPr, RЈ = Ph,

C₆F₅).^[10,11]Compounds 6a and 6b are air-stable both in

solution and in the solid state and were characterized by

¹H, ¹³C{¹H}, and ³¹P{¹H} NMR spectroscopy as well as

elemental analysis.

Figure 8. Structural view of [RuCp*{η¹-(N)-NnPrPPh₂-η⁴-

CH=C(CH₂)₄CH=CH₂}]PF₆(6b) showing 20% thermal ellipsoids

–

(PF₆omitted for clarity; only the first of three independent Ru

complexes is shown). Selected bond lengths [Å]: Ru–C(1–5)_av

2.220(2), Ru–N 2.184(2), Ru–C(26) 2.191 (2), Ru–C(27) 2.249(2),

Ru–C(32) 2.244(2), Ru–C(33) 2.172(2), P(1)–N 1.600(2), P(1)–

C(26) 1.771(2), C(26)–C(27) 1.423(3), C(27)–C(32) 1.436(3), C(32)–

C(33) 1.406(4).

In similar fashion to the RuCp complexes 1a–c, with 1,6-

heptadiyne, 1,7-octadiyne, 2b, and 2c, the η¹-phosphaallyl–

η³-azaallyl complexes [RuCp*{η¹-(P)-PPh₂–CH=C(CH₂)₃-

η³-(C,C,N)-CCHNEt₂}]PF₆(8a), [RuCp*{η¹-(P)-PPh₂–

CH=C(CH₂)₃-η³-(C,C,N)-CCHNC₅H₁₀}]PF₆(8b), [RuCp*-

{η¹-(P)-PPh₂–CH=C(CH₂)₄-η³-(C,C,N)-CCHNEt₂}]PF₆

(8c), and [RuCp*{η¹-(P)-PPh₂–CH=C(CH₂)₄-η³-(C,C,N)-

CCHNC₅H₁₀}]PF₆(8d), respectively, are obtained in high

isolated yields (Scheme 4). While in the case of 1,6-hep-

tadiyne the intermediacy of η³-phosphaallyl–η²-vinylamine

Scheme 3.

As these compounds exhibit similar spectroscopic fea- complexes 7a and 7b could be observed by NMR spec-

tures to the RuCp η⁴-butadiene amido complexes already troscopy, in the case of 1,7-octadiyne no intermediates were

described recently,^[10,11]they are not discussed here. The so- detected. Again, all compounds were fully characterized by

1

lid-state structures of 6a and 6b were determined by single- a combination of H, ¹³C{¹H}, and ³¹P{¹H} NMR spec-

crystal X-ray diffraction. ORTEP diagrams are depicted in troscopy and elemental analysis. Overall, the spectroscopic

Figure 7 and Figure 8 with selected bond lengths reported features of complexes 7 and 8 are very similar to those of

in the captions.

complexes 3 and 4 and are thus not discussed here. In ad-

Eur. J. Inorg. Chem. 2006, 1006–1021

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1011

S. Pavlik, F. Jantscher, G. Dazinger, K. Mereiter, K. Kirchner

FULL PAPER

dition, the solid-state structures of 8c and 8d were deter-

mined by single-crystal X-ray diffraction. ORTEP plots are

depicted in Figure 9 and Figure 10 with selected bond

lengths reported in the captions.

Figure 10. Structural view of [RuCp*{η¹-(P)-PPh₂CH=C(CH₂)₄-

η³-(C,C,N)-C=CH–N(CH₂)₅}]PF₆(8d) showing 30% thermal ellip-

–

soids (PF₆omitted for clarity). Selected bond lengths [Å]: Ru–

C(1–5)_av2.228(2), Ru–P(1) 2.2978(5), Ru–C(29) 2.252(2), Ru–C(30)

2.090(2), Ru–N 2.233(2), P(1)–C(23) 1.796(2), C(23)–C(24)

1.326(3), C(24)–C(29) 1.508(3), C(29)–C(30) 1.418(3), N–C(30)

1.418(2).

at room temperature yields, upon workup, a 5:1 mixture

of [RuCp{κ¹(P)-PPh₂NHNMe₂}(CH₃CN)₂]PF₆(9) and

[RuCp{κ²(P,N)-PPh₂NHNMe₂}(CH₃CN)]PF₆(10) where

the PPh₂NHNMe₂ligand is attached to the metal center in

the κ¹-P and κ²-P,N mode, respectively (Scheme 5). Com-

plex 9 is obtained in pure form, when the reaction is per-

formed in the presence of 1 equiv. of CH₃CN. Both com-

Scheme 4.

1

plexes were characterized by means of H, ¹³C{¹H}, and

³¹P{¹H} NMR spectroscopy and elemental analysis in the

case of 9. Crystals of 10 could be grown by diffusion of

diethyl ether into a CH₂Cl₂solution of a reaction mixture

containing both 9 and 10. A structural view of 10 is de-

picted in Figure 11 with selected bond lengths and angles

reported in the caption.

Figure 9. Structural view of [RuCp*{η¹-(P)-PPh₂CH=C(CH₂)₄-η³-

(C,C,N)-C=CH–NEt₂}]PF₆·CH₂Cl₂(8c·CH₂Cl₂) showing 30%

–

thermal ellipsoids (PF₆and solvent omitted for clarity). Selected

Scheme 5.

bond lengths [Å]: Ru–C(1–5)_av2.239(2), Ru–P(1) 2.3020(6), Ru–

C(29) 2.253(2), Ru–C(30) 2.092(2), Ru–N 2.243(2), P(1)–C(23)

1.795(2), C(23)–C(24) 1.325(3), C(24)–C(29) 1.510(3), C(29)–C(30)

1.425(3), N–C(30) 1.421(3).

Complexes 9 and 10 exhibit singlet resonances in the

³¹P{¹H} NMR spectrum at 90.6 to 61.4 ppm, respectively.

In the case of 10 where the PPh₂NHNMe₂ligand is bound

Finally, as part of our ongoing effort to investigate the in κ²-P,N fashion the¹H and ¹³C{¹H} NMR spectra show

chemistry of complexes with ligands which possess direct the two methyl groups to be inequivalent, giving rise to two

P^III–N bonds towards alkynes, we set out here to prepare a signals at δ = 3.35 and 2.82 ppm and 63.9 and 57.8 ppm,

complex with a diphenylphosphanylhydrazide ligand, that respectively [cf. complex 9 exhibits one singlet at δ =

is, a ligand having a P^III–N–N unit. It should be noted that 2.27 ppm and a doublet centered at δ = 49.9 ppm (J_CP

transition-metal complexes with R₂PNHNRЈ₂ligands are 3.4 Hz)].

=

comparatively rare. With respect to late transition metals,

Unfortunately, in contrast to the clean reactions of com-

they have been found to coordinate either as monodentate plexes 1 and 2 with diynes, the reaction of 9 with 1,6-hep-

or bidentate ligands in κ¹-P and κ²-P,N fashion, respec- tadiyne and 1,7-octadiyne afforded only mixtures of intrac-

tively.^[18]Accordingly, treatment of [RuCp(CH₃CN)₃]PF₆table materials. Thus as yet no further reactions have been

with 1 equiv. of PPh₂NHNMe₂in CH₂Cl₂as the solvent performed with 9.

1012

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Eur. J. Inorg. Chem. 2006, 1006–1021

Reactions of Ruthenium–Aminophosphane Complexes with Diynes

FULL PAPER

triene A and the η³-allyl carbene complex B. The formation

of the latter involves migration of the κ¹(P) coordinated

PPh₂NRRЈ ligand to one of the two electrophilic carbene

carbon atoms of A.^[19]Accordingly, we have chosen B (in

the form of the two model complexes [CpRu{=CH–(η³-

CHCHCH–PH₂NH₂)}]⁺and [CpRu{=CH-(η³-CHCHCH–

PMe₂NHMe)}]⁺) as the starting point of our theoretical

mechanistic investigation based on DFT/B3LYP calcula-

tions. The energy profile for the conversion of B to the η³-

phosphaallyl–η²-vinylamine complexes 4 is shown in Fig-

ure 12. The models of 4 with PH₂NH₂and PMe₂NHMe

will be called F (in Figure 12 the energy values in parenthe-

ses refer to PMe₂NHMe). The reliability of the computa-

tional method (details in Experimental Section) is sup-

ported by the good agreement between the calculated ge-

ometries of F with the X-ray structures of the related com-

plexes (e.g. 3a and 3c).

Figure 11. Structural view of [RuCp{κ²-(P,N)-PPh₂NH-

NMe₂}(CH₃CN)]PF₆(10) showing 30% thermal ellipsoids (PF₆

omitted for clarity). Selected bond lengths [Å] and angles [°]: Ru–

C(1–5)_av2.173(2), Ru–P(1) 2.2915(2), Ru–N(2) 2.216(2), Ru–N(3)

2.050(2), P(1)–N(2) 1.688(2), N(1)–N(2) 1.456(2), P(1)–Ru–N(2)

67.03(4).

–

The first step B to C constitutes a rotation of the amino-

phosphane substituent about the C–P bond, which is re-

quired to place the amine moiety in a position suitable for

nucleophilic attack at the carbene carbon atom. This pro-

cess is slightly endothermic by 3.2 kcal/mol and possesses a

small activation barrier (6.7 kcal/mol). Subsequent nucleo-

Mechanistic Aspects

For the present conversion of 1 and 2 to the respective philic attack of the amine moiety at the carbene carbon

phosphaallyl complexes 4, unfortunately, no intermediate atom of C yields intermediate D, which features an unusual

products could be detected spectroscopically. From pre- six-membered aza-phosphacycle. The transition state for

vious experimental data^[19]it is reasonable to assume that this process, TS_CD, is very similar to the structure of D,

the formation of the η³-phosphaallyl–η²-vinylamine pro- indicating that the transition state structure occurs quite

ceeds via the intermediacy of the cationic metallacylopenta- late along the reaction coordinate and is merely 0.3 kcal/

Figure 12. Energy profile (in kcal/mol, relative to B) for the conversion of B to F with PH₂NH₂as model aminophosphane ligand. The

numbers in parentheses refer to PMe₂NHMe as the model ligand.

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S. Pavlik, F. Jantscher, G. Dazinger, K. Mereiter, K. Kirchner

FULL PAPER

mol higher in energy than D. In the course of this reaction, ceeds most likely again via the intermediacy of E (Fig-

a new N···C bond starts to form. It is 1.78 Å in TS_CDand ure 12). This first step needs an activation energy of

finally reaches 1.58 Å in species D. This process requires an 26.3 kcal/mol for the parent PH₂NH₂ligand and 24.5 kcal/

activation energy of 17.9 kcal/mol. The P–N bond in D is mol for PMe₂NHMe and is thus rate determining. Once E

rather weak as judged from the long P–N bond length of is re-formed, the subsequent processes are facile. Complex

1.81 Å. Accordingly, this bond is readily cleaved, yielding E proceeds through transition state TS_EGto afford the

the η³-phosphaallyl–η²-vinylamine complex E. This trans- metallacycle G. This reaction is energetically slightly unfa-

formation is strongly exothermic, releasing 44.9 kcal/mol. vorable by 6.7 kcal/mol with an activation energy of

The transition state connecting D and E is reached at an 12.1 kcal/mol. These values, however, are comparatively

early stage and thus its structure is very similar to D. In small taking into account that in the course of this reaction

fact, the only noticeable change from D to TS_DEis a weak two Ru–C bonds are broken, which are counterbalanced

but apparently important Ru···P interaction of 2.88 Å. In E only by one weak Ru–C interaction (2.65 Å). Moreover, as

the Ru–P bond is fully developed (2.30 Å), while the Ru– a consequence of that ongoing from E by TS_EGto G, the

C⁴bond becomes very weak or almost nonbonding C4 chain experiences a severe distortion, as is apparent

(2.95 Å). On going from D to E, the amino substituent is from the changes of the respective torsion angles C–C–C–

initially placed in an anti position, that is, pointing towards C being 39.2, 58.1, and finally 111.5°, respectively. This may

the phosphane moiety, which is sterically unfavorable, espe- also explain why the formation of azaallyl complexes is far

cially if the amine is mono- or even disubstituted (repulsive more facile in the case of 1,7-octadiyne where the phos-

interactions) such as in 3b, 3c, 3d, or 3e. Rotation of the phaallyl complexes contain a six-membered ring system

amine unit about the C³–C⁴bond yields the experimentally than with 1,6-heptadiyne where these complexes feature a

observed and isolated syn isomer F. Surprisingly, despite the more rigid five-membered ring. The subsequent conversion

fact that the Ru–C⁴bond is rather long (2.95 Å), the acti- of G to the η¹-phosphaallyl–η³-azaallyl complexes H re-

vation barrier for this rotation is relatively high, requiring quires merely 0.4 kcal/mol activation energy and is energeti-

22.4 kcal/mol. However, in the case of the more realistic cally very favorable, releasing 18.5 kcal/mol (Figure 13).

model ligand PMe₂NHMe, the activation barrier becomes

Finally, we also looked for a plausible mechanism of the

significantly smaller (14.5 kcal/mol) and unfavorable steric formation of amido-butadiene complexes (I) from allyl car-

interactions are better taken into account (Figure 12, num- bene complexes (B). This reaction is obviously restricted to

bers in parentheses).

aminophosphane ligands possessing NH protons. An ener-

Experimentally it has been observed that η³-phosphaal- getically feasible pathway with the model complexes [CpRu-

lyl–η²-vinylamine complexes (F) are the kinetic products {=CH-(η³-CHCHCH–PH₂NH₂)}]⁺and [CpRu{=CH-(η³-

but isomerize (in some cases already at room temperature) CHCHCH–PMe₂NHMe)}]⁺(A) is shown in Figure 14. Ac-

to the thermodynamically more stable η¹-phosphaallyl–η³- cordingly, the N–H proton in B is transferred to the carbene

azaallyl complexes H. The energy profiles for this conver- carbon atom by transition state TS_HIwithout any involve-

sion are presented in Figures 12 (F Ǟ E) and 13 (E Ǟ H). ment of the metal center. This reaction has an activation

In agreement with experimental data, the overall process is barrier of 17.7 kcal/mol (18.1 kcal/mol for PMe₂NHMe)

thermodynamically favored. This rearrangement exhibits a and is exothermic releasing 8.4 kcal/mol (11.0 kcal/mol for

syn–anti isomerization of the NH₂substituent and thus pro- PMe₂NHMe). Therefore, in the case of complexes with

Figure 13. Energy profile (in kcal/mol, relative to B) for the conversion of E to H with PH₂NH₂as model aminophosphane ligand. The

numbers in parentheses refer to PMe₂NHMe as the model ligand.

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Reactions of Ruthenium–Aminophosphane Complexes with Diynes

FULL PAPER

[RuCp(PPh₂NEt₂)(CH₃CN)₂]PF₆(1b): This complex has been pre-

pared analogously to 1a with [RuCp(CH₃CN)₃]PF₆(300 mg,

0.69 mmol) and PPh₂NEt₂(179 mg, 0.69 mmol) as starting materi-

als. Yield: 416 mg (93%). C₂₅H₃₁F₆N₃P₂Ru (650.55): calcd. C

46.16, H 4.80, N 6.46; found C 46.10, H 4.72, N 6.55. ¹H NMR

(CD₂Cl₂, 20 °C): δ = 7.61–7.30 (m, 10 H, Ph), 4.26 (s, 5 H, Cp),

aminophosphanes that contain N–H bonds, this pathway

becomes competitive with the formation of phosphaallyl (F)

and azaallyl complexes (H). It should be noted that we were

unable to find an alternative pathway to obtain amido buta-

diene complexes by oxidative addition of the N–H bond to

the metal center.

3.42–3.20 (m, 4 H, Et), 2.22 (6 H, CH₃CN), 0.96 (t, J_HH= 7.1 Hz,

1

3 H, Et) ppm. ¹³C{¹H} NMR (δ, CD₂Cl₂, 20 °C): 137.4 (d, J_CP

=

2

4

46.0 Hz, Ph¹), 131.4 (d, J_CP= 11.5 Hz, Ph^2,6), 129.7 (d, J_CP

1.9 Hz, Ph⁴), 128.0 (d, J_CP= 9.6 Hz, Ph^3,5), 127.3 (CH₃CN), 77.4

3

(d, J_CP= 2.3 Hz, Cp), 42.4 (d, J_CP= 6.5 Hz, CH₂), 13.6 (d, J_CP

=

2.3 Hz, CH₃), 3.7 (CH₃CN) ppm. ³¹P{¹H} NMR (δ, CD₂Cl₂,

20 °C): 102.1 (PPh₂), –143.0 (¹J_FP= 711.8 Hz, PF₆) ppm.

[RuCp(PPh₂NC₅H₁₀)(CH₃CN)₂]PF₆(1c): This complex has been

prepared analogously to 1a with [RuCp(CH₃CN)₃]PF₆(374 mg,

0.86 mmol) and PPh₂NC₅H₁₀(232 mg, 0.86 mmol) as starting ma-

terials. Yield: 500 mg (88%). C₂₆H₃₁F₆N₃P₂Ru (662.56): calcd. C

47.13, H 4.72, N, 6.34; found C 46.66, H 4.89, N 6.51. ¹H NMR

(CD₂Cl₂, 20 °C): δ = 7.66–7.26 (m, 10 H, Ph), 4.23 (s, 5 H, Cp),

3.30–3.01 (m, 4 H, NC₅H₁₀), 2.20 (d, J_HP= 1.0 Hz, 6 H, CH₃CN),

1.72–1.36 (m, 6 H, NC₅H₁₀) ppm. ¹³C{¹H} NMR (CD₂Cl₂, 20 °C):

δ = 136.6 (d, ¹J_CP= 46.0 Hz, Ph¹), 131.2 (d, ²J_CP= 11.1 Hz, Ph^2,6),

129.7 (d, ⁴J_CP= 1.9 Hz, Ph⁴), 128.1 (d, ³J_CP= 9.6 Hz, Ph^3,5), 127.3

(CH₃CN), 77.4 (d, J_CP= 2.3 Hz, Cp), 50.1 (d, J_CP= 3.4 Hz, CH₂),

27.0 (d, J_CP= 5.4 Hz, CH₂), 24.4 (CH₂), 3.7 (CH₃CN) ppm.

³¹P{¹H} NMR (CD₂Cl₂, 20 °C): δ = 98.8 (PPh₂), –143.0 (¹J_FP

710.5 Hz, PF₆) ppm.

=

Figure 14. Energy profile (in kcal/mol, relative to B) for the reac-

tion of B to I with PH₂NH₂as model aminophosphane ligand. The

numbers in parentheses refer to PMe₂NHMe as the model ligand.

[RuCp*(PPh₂NHnPr)(CH₃CN)₂]PF₆(2a): PPh₂NHnPr (145 mg

0.60 mmol) was added to a solution of [RuCp*(CH₃CN)₃]PF₆

(300 mg, 0.60 mmol) in CH₂Cl₂(5 mL) and the mixture was stirred

for 2 h at room temperature. The volume of the solution was then

reduced to about 1 mL and Et₂O (5 mL) was added. A yellow pre-

cipitate was formed, which was washed with Et₂O (2×5 mL) and

dried under vacuum. Yield: 336 mg (80%) C₂₉H₃₉F₆N₃P₂Ru

(706.66): calcd. C 49.29, H 5.56, N 5.95; found: C 48.94,; H 6.09,

Experimental Section

General: Manipulations were performed under inert purified argon

by using Schlenk techniques and/or a glovebox. All chemicals were

standard reagent grade and used without further purification. The

solvents were purified according to standard procedures.^[20]The

deuterated solvents were purchased from Aldrich and dried with

1

N 5.59. H NMR (CD₂Cl₂, 20 °C): δ = 7.65–7.40 (m, 10 H, Ph),

3.09–2.85 (m, 1 H, NH), 2.74 (m, J_HH= 6.9 Hz, 2 H, CH₂), 2.23

(d, J_HP= 1.3 Hz, 6 H, CH₃CN), 1.49 (d, J_HP= 1.7 Hz, 15 H, Cp*),

1.27–1.21 (m, 2 H, CH₂), 0.84 (t, J_HH= 7.5 Hz, 3 H, CH₃) ppm.

¹³C{¹H} NMR (CD₂Cl₂, 20 °C): δ = 135.4 (d, ¹J_CP= 43.7 Hz, Ph¹),

4 Å molecular sieves. [RuCp(CH₃CN)₃]PF₆,^[21][RuCp*(CH₃CN)₃]-

PF₆,^[22]and PPh₂NHNMe₂

were prepared according to the lit-

[23]

2

3

132.0 (d, J_CP= 11.5 Hz, Ph^2,6), 129.7 (Ph⁴), 128.0 (d, J_CP

=

erature. ¹H, ¹³C{¹H}, and ³¹P{¹H} NMR spectra were recorded

with Bruker Avance-250 and -300 spectrometers and were refer-

enced to SiMe₄and H₃PO₄(85%), respectively. ¹H and ¹³C{¹H}

NMR signal assignments were confirmed by ¹H-COSY, 135-DEPT,

and HSQC(¹H-¹³C) experiments.

9.2 Hz, Ph^3,5), 124.7 (CH₃CN), 86.8 (Cp*), 46.0 (d, J_CP= 9.2 Hz,

CH₂), 25.0 (d, J_CP= 6.1 Hz, CH₂), 10.5 (CH₃), 9.1 (Cp*), 3.8

(CH₃CN) ppm. ³¹P{¹H} NMR (CD₂Cl₂, 20 °C): δ = 82.9 (PPh₂),

–144.5 (¹J_FP= 710.2 Hz, PF₆) ppm.

[RuCp*(PPh₂NEt₂)(CH₃CN)₂]PF₆(2b): This complex has been pre-

pared analogously to 2a with [RuCp*(CH₃CN)₃]PF₆(300 mg,

0.60 mmol) and PPh₂NEt₂(153 mg 0.60 mmol) as starting materi-

als. Yield: 350 mg (82%) C₃₀H₄₁F₆N₃P₂Ru (720.68): calcd. C 50.00,

H 5.73, N 5.83; found C 50.24, H 5.44, N 5.59. ¹H NMR (CD₂Cl₂,

20 °C): δ = 7.58–7.18 (m, 10 H, Ph), 3.30–3.13 (m, 4 H, CH₂), 2.74

[RuCp(PPh₂NHnPr)(CH₃CN)₂]PF₆(1a): PPh₂NHnPr (185 mg,

0.76 mmol) was added to a solution of [RuCp(CH₃CN)₃]PF₆

(300 mg, 0.69 mmol) in CH₂Cl₂(10 mL) and the mixture was

stirred for 2 h at room temperature. After removal of the solvent,

a yellow powder was obtained which was collected on a glass frit,

washed with Et₂O (3×10 mL), and dried under vacuum. Yield:

421 mg (95%). C₂₄H₂₉F₆N₃P₂Ru (636.52): calcd. C 45.29, H 4.59,

3

(m, J_HH= 6.9 Hz, 2 H, CH₂), 2.24 (d, J_HP= 1.1 Hz, 6 H,

3

CH₃CN), 1.32 (d, J_HP= 1.7 Hz, 15 H, Cp*Ј), 1.00 (t, J_HH

=

1

N 6.60; found C 45.23, H 4.79, N 6.74. H NMR (CD₂Cl₂, 20 °C):

7.1 Hz, 6 H, CH₃) ppm. ¹³C{¹H} NMR (CD₂Cl₂, 20 °C): δ = 136.7

δ = 7.69–7.42 (m, 10 H, Ph), 4.43 (s, 5 H, Cp), 2.85–2.66 (m, 2 H,

nPr), 2.50–2.32 (m, 1 H, NHnPr), 2.20 (d, J_HP= 1.4 Hz, 6 H,

CH₃CN), 1.51 –1.30 (m, 2 H, nPr), 0.80 (t, J_HH= 7.4 Hz, 3 H, nPr)

ppm. ¹³C{¹H} NMR (CD₂Cl₂, 20 °C): δ = 136.1 (d, ¹J_CP= 48.7 Hz,

(d, J_CP= 41.4 Hz, Ph¹), 131.8 (d, J_CP= 11.5 Hz, Ph^2,6), 129.4

1

2

(Ph⁴), 127.9 (d, J_CP= 9.2 Hz, Ph^3,5), 125.5 (CH₃CN), 87.2 (Cp*),

3

41.6 (d, J_CP= 7.7 Hz, CH₂), 12.9 (d, J_CP= 3.1 Hz, CH₃), 8.7 (Cp*),

3.8 (CH₃CN) ppm. ³¹P{¹H} NMR (CD₂Cl₂, 20 °C): δ = 101.3

(PPh₂), –144.4 (¹J_FP= 712.0 Hz, PF₆) ppm.

Ph¹), 131.6 (d, ²J_CP= 11.9 Hz, Ph^2,6), 130.0 (d, ⁴J_CP= 1.9 Hz, Ph⁴),

3

128.2 (d, J_CP= 10.0 Hz, Ph^3,5), 126.7 (CH₃CN), 76.6 (d, J_CP

=

2.3 Hz, Cp), 45.8 (d, J_CP= 8.0 Hz, CH₂), 24.9 (d, J_CP= 5.8 Hz,

[RuCp*(PPh₂NC₅H₁₀)(CH₃CN)₂]PF₆(2c): This complex has been

CH₂), 11.0 (CH₃), 3.7 (CH₃CN) ppm. ³¹P{¹H} NMR (CD₂Cl₂, prepared analogously to 2a with [RuCp*(CH₃CN)₃]PF₆(300 mg,

20 °C): δ = 86.0 (PPh₂), –143.0 (¹J_FP= 708.3 Hz, PF₆) ppm.

0.60 mmol) and PPh₂NC₅H₁₀(160 mg 0.60 mmol) as starting mate-

Eur. J. Inorg. Chem. 2006, 1006–1021

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1015

S. Pavlik, F. Jantscher, G. Dazinger, K. Mereiter, K. Kirchner

FULL PAPER

rials. Yield: 380 mg (87%) C₃₁H₄₁F₆N₃P₂Ru (732.69): calcd. C

3

(d, J_CP= 12.3 Hz, Ph^3,5), 129.7 (d, J_CP= 12.3 Hz, Ph^3,5), 129.0

3

1

50.82, H 5.64, N 5.74; found C 50.14, H 5.46, N 5.78. ¹H NMR (d, J_CP= 12.3 Hz, Ph^3Ј,5Ј), 126.5 (d, J_CP= 50.6 Hz, Ph¹), 117.8

(CD₂Cl₂, 20 °C): δ = 7.51–7.35 (m, 10 H, Ph), 3.06–2.90 (m, 4 H,

CH₂), 2.24 (d, J_HP= 1.26 Hz, 6 H, CH₃CN), 1.62–1.48 (m, 6 H, 1.5 Hz, Cp), 76.1 (C²), 52.4 (CH₂), 41.3 (d, J_CP= 24.2 Hz, C¹),

CH₂), 1.32 (d, J_HP= 1.7 Hz, 15 H, Cp*Ј) ppm. ¹³C{¹H} NMR

35.7 (d, J_CP= 6.9 Hz, CH₂), 33.3 (CH₂), 24.9 (CH₂), 23.2 (CH₂),

(d, J_CP= 3.8 Hz, C³), 116.8 (d, J_CP= 5.8 Hz, C⁴), 79.1 (d, J_CP

=

(CD₂Cl₂, 20 °C): δ = 135.8 (d, J_CP= 40.6 Hz, Ph¹), 131.5 (d, J_CP23.1 (CH₂) ppm. ³¹P{¹H} NMR (CD₂Cl₂, 20 °C): δ = 8.1 (PPh₂),

1

2

= 10.7 Hz, Ph^2,6), 129.3 (Ph⁴), 128.0 (d, ³J_CP= 9.2 Hz, Ph^3,5), 125.3

–142.9 (¹J_FP= 710.8 Hz, PF₆) ppm.

(CH₃CN), 87.2 (Cp*), 50.4 (d, J_CP= 3.8 Hz, CH₂), 26.9 (d, J_CP

=

Reaction of 1b with 1,7-Octadiyne in CD₂Cl₂. Formation of

[RuCp{η³-(P,C,C)–PPh₂–CH–C(CH₂)₄-η²-(C,C)-CCHNEt₂}]PF₆

(3d) and [RuCp{η¹-(P)-PPh₂–CH=C(CH₂)₄-η³-(C,C,N)-

CCHNEt₂}]PF₆(4e): A 5-mm NMR tube was charged with 1b

(30 mg, 0.05 mmol) in CD₂Cl₂(0.5 mL) and 1,7-octadiyne (6,1 µL,

0.05 mmol) was added by syringe. The reaction was then monitored

6.9 Hz, CH₂), 24.3 (CH₂), 8.7 (Cp*), 3.8 (CH₃CN) ppm. ³¹P{¹H}

NMR (CD₂Cl₂, 20 °C): δ = 96.1 (PPh₂), –144.4 (¹J_FP= 710.8 Hz,

PF₆) ppm.

[RuCp{η³-(P,C,C)-PPh₂CHC–(CH₂)₃–η²-(C,C)-CCHNHnPr}]PF₆

(3a): 1.1 equiv. of 1,6-heptadiyne (26.7 µL, 0.23 mmol) was added

to a solution of 1a (135 mg, 0.21 mmol) in CH₂Cl₂(10 mL) and

the mixture was stirred for 2 h at room temperature. After removal

of the solvent under reduced pressure, an orange solid was ob-

tained, which was washed with Et₂O (5 mL), and dried under vac-

uum. Yield: 99 mg (73 %). C₂₇H₃₁F₆NP₂Ru (646.56): calcd. C

50.16, H 4.83, N 2.17; found C 49.88, H 5.02, N 2.22. ¹H NMR

(CD₂Cl₂, 20 °C): δ = 7.79–7.25 (m, 10 H, Ph), 5.05 (s, 5 H, Cp),

4.30–4.09 (m, 1 H, NHnPr), 4.14 (d, ²J_HP= 5.4 Hz, 1 H, H¹), 3.99

(d, J_HP= 7.6 Hz, 1 H, H⁴), 3.37–3.20 (m, 1 H), 2.97–2.66 (m, 3 H),

2.62–2.39 (m, 2 H), 2.36–2.17 (m, 1 H), 2.09–1.86 (m, 1 H), 1.46–

1.08 (m, 2 H), 0.77 (t, J_HH= 7.4, 3 H) ppm. ¹³C{¹H} NMR

(CD₂Cl₂, 20 °C): δ = 133.8 (d, ²J_CP= 11.5 Hz, Ph^2,6), 132.4 (d, ²J_CP

1

by H and ³¹P{¹H} NMR spectroscopy. After 20 min both 3d and

4e were formed in an approximately 3:1 ratio. After 5 h this ratio

changed to about 1:6. Because of spectral overlap with 4e only the

most characteristic signals of 3d could be unequivocally assigned.

2

¹H NMR (CD₂Cl₂, 20 °C): δ = 5.10 (s, 5 H, Cp), 3.53 (d, J_HP

=

4.7 Hz, 1 H, H¹), 2.90 (d, J_HP= 7.6 Hz, 1 H, H⁴), 0.83 (t, J_HH

7.1 Hz, 6 H, Et) ppm. ³¹P{¹H} NMR (CD₂Cl₂, 20 °C): δ = 3.3

(PPh₂), –143.0 (¹J_FP= 710.8 Hz, PF₆) ppm. After heating at 40 °C

for 8 h, the 3d was completely converted to 4e.

Reaction of 1c with 1,7-Octadiyne in CD₂Cl₂. Formation of [RuCp-

{η³-(P,C,C)–PPh₂–CH–C(CH₂)₄-η²-(C,C)-CCHNC₅H₁₀}]PF₆(3e)

a n d [ Ru C p { η ¹- ( P ) - P P h ₂– C H = C ( C H₂)₄- η ³- (C, C, N )-

CCHNC₅H₁₀}]PF₆(4f): A 5-mm NMR tube was charged with 1c

(34 mg, 0.05 mmol) in CD₂Cl₂(0.5 mL) and 1,7-octadiyne (6,1 µL,

0.05 mmol) was added by syringe. The reaction was then monitored

4

= 12.3 Hz, Ph^2Ј,6Ј), 131.6 (d, J_CP= 3.4 Hz, Ph⁴), 131.7–131.6 (d,

⁴J_CP= 3.4 Hz, Ph^4Ј), 129.9 (d, ³J_CP= 12.3 Hz, Ph^3,5), 129.1 (d, ³J_CP

1

= 12.3 Hz, Ph^3Ј,5Ј), 122.1 (d, J_CP= 52.1 Hz, Ph¹), 116.8 (d, J_CP

=

3.8 Hz, C³), 106.9 (d, J_CP= 6.1 Hz, C⁴), 82.1 (C²), 81.7 (Cp), 50.4

(CH₂), 41.6 (d, J_CP= 24.5 Hz, C¹), 37.1 (d, J_CP= 7.7 Hz, CH₂),

31.6 (CH₂), 22.6 (CH₂), 21.9 (CH₂), 11.8 (CH₃) ppm. ³¹P{¹H}

NMR (CD₂Cl₂, 20 °C): δ = 9.3 (PPh₂), –142.9 (¹J_FP= 711.5 Hz,

PF₆) ppm.

1

by H and ³¹P{¹H} NMR spectroscopy. After 30 min both 3e and

4f were formed in an approximately 8:1 ratio. After 5 h this ratio

changed to about 3:1. Because of spectral overlap with 4f only the

most characteristic signals of 3e could be unequivocally assigned.

2

¹H NMR (CD₂Cl₂, 20 °C): δ = 5.20 (s, 5 H, Cp), 3.51 (d, J_HP

=

5.1 Hz, 1 H, H¹), 2.62 (d, J_HP= 7.0 Hz, 1 H, H⁴) ppm. ³¹P{¹H}

NMR (CD₂Cl₂, 20 °C): δ = 7.9 (PPh₂), –142.9 (¹J_FP= 710.8 Hz,

PF₆) ppm. After heating at 40 °C for 8 h, 3e was completely con-

verted to 4f.

[RuCp{η³-(P,C,C)-PPh₂CHC–(CH₂)₃–η²-(C,C)-CCHNEt₂}]PF₆

(3b): This complex has been prepared analogously to 3a with 1b

(100 mg, 0.15 mmol) and 1,6-heptadiyne (19.5 µL, 0.17 mmol) as

the starting materials. Yield: 75 mg (76 %). C₂₈H₃₃F₆NP₂Ru

(660.58): calcd. C 50.91, H 5.09, N 2.12; found C 50.83, H 5.11, N

2.19. ¹H NMR (CD₂Cl₂, 20 °C): δ = 7.68–7.41 (m, 10 H, Ph), 5.09

(s, 5 H, Cp), 4.01 (d, ²J_HP= 4.7 Hz, 1 H, H¹), 3.58 (d, J_HP= 5.7 Hz,

1 H, H⁴), 3.01–2.86 (m, 2 H), 2.82–2.51 (m, 6 H), 2.39–2.27 (m, 2

H), 0.96 (t, J_HH= 7.1 Hz, 3 H) ppm. ¹³C{¹H} NMR (CD₂Cl₂,

[RuCp{η¹-(P)-PPh₂CH=C–(CH₂)₃–η³-(C,C,N)-CCHNHnPr}]PF₆

(4a): A stirred solution of 3a (50 mg, 0,08 mmol) in CH₃NO₂

(5 mL) was kept at 90 °C for 3 h. After removal of the solvent un-

der reduced pressure, an orange solid was obtained which was

washed with Et₂O (5 mL), and dried under vacuum. Yield: 37 mg

(73%). C₂₇H₃₁F₆NP₂Ru (646.56): calcd. C 50.16, H 4.83, N 2.17;

found C 49.68, H 4.82, N 2.23. ¹H NMR (CD₃NO₂, 20 °C): δ =

8.01–7.87 (m, 2 H, Ph), 7.68–7.45 (m, 6 H, Ph), 7.33–7.18 (m, 2 H,

Ph), 6.02 (1 H, H⁴), 5.98 (d, J_HP= 10.1 Hz, 1 H, H¹), 4.85 (s, 5 H,

Cp), 3.06–2.89 (m, 1 H), 2.86–2.40 (m, 5 H), 2.21–2.00 (m, 2 H),

1.47–1.11 (m, 2 H), 0.59 (t, J_HH= 7.4 Hz, 3 H) ppm. The NH

proton could not be detected. ¹³C{¹H} NMR (CD₃NO₂, 20 °C): δ

2

20 °C): δ = 133.2 (d, J_CP= 11.9 Hz, Ph^2,6), 132.4 (d, J_CP

=

4

12.3 Hz, Ph^2Ј,6Ј), 132.1 (d, J_CP= 3.5 Hz, Ph⁴), 131.6 (d, J_CP

2.3 Hz, Ph^4Ј), 129.8 (d, J_CP= 11.5 Hz, Ph^3,5), 129.0 (d, J_CP

3

1

11.9 Hz, Ph^3Ј,5Ј), 125.9 (d, J_CP= 47.9 Hz, Ph¹), 117.8 (d, J_CP

6.9 Hz, C⁴), 117.4 (d, J_CP= 4.6 Hz, C³), 79.1 (d, J_CP= 1.5 Hz, Cp),

75.8 (C²), 46.8 (CH₂), 40.8 (d, J_CP= 24.2 Hz, C¹), 36.0 (d, J_CP

=

7.3 Hz, CH₂), 33.2 (CH₂), 23.1 (CH₂), 12.1 (CH₃) ppm. ³¹P{¹H}

NMR (CD₂Cl₂, 20 °C): δ = 4.2 (PPh₂), –143.0 (¹J_FP= 710.8 Hz,

PF₆) ppm.

1

= 170.1 (d, J_CP= 29.1 Hz, C³), 136.4 (d, J_CP= 52.1 Hz, Ph¹),

134.2 (d, ²J_CP= 11.5 Hz, Ph^2,6), 131.3 (d, ⁴J_CP= 2.3 Hz, Ph⁴), 131.2

1

2

(d, J_CP= 41.4 Hz, Ph^1Ј), 130.4 (d, J_CP= 11.1 Hz, Ph^2Ј,6Ј), 130.0

[RuCp{η³-(P,C,C)-PPh₂CHC–(CH₂)₃–η²-(C,C)-CCHNC₅H₁₀}]PF₆

(3c): This complex has been prepared analogously to 3a with 1c

(105 mg, 0.16 mmol) and 1,6-heptadiyne (19 µL, 0.17 mmol) as the

starting materials. Yield: 74 mg (69%). C₂₉H₃₃F₆NP₂Ru (672.59):

4

3

(d, J_CP= 2.7 Hz, Ph^4Ј), 128.8 (d, J_CP= 10.4 Hz, Ph^3,5), 128.7 (d,

³J_CP= 11.1 Hz, Ph^3Ј,5Ј), 111.9 (d, J_CP= 47.2 Hz, C¹), 85.8 (d, J_CP

= 1.9 Hz, C²), 81.3 (d, J_CP= 1.9 Hz, Cp), 74.4 (C⁴), 57.5 (CH₂),

35.6 (CH₂), 28.9 (d, J_CP= 19.2 Hz, CH₂), 25.2 (CH₂), 24.1 (CH₂),

9.6 (CH₃) ppm. ³¹P{¹H} NMR (CD₃NO₂, 20 °C): δ = 70.3

(PPh₂), –143.2 (¹J_FP= 707.4 Hz, PF₆) ppm.

1

calcd. C 51.79, H 4.95, N 2.08; found C 51.87, H 5.09, N 2.14. H

NMR (CD₂Cl₂, 20 °C): δ = 7.72–7.31 (m, 10 H, Ph), 5.14 (s, 5 H,

2

Cp), 4.03 (d, J_HP= 4.7 Hz, 1 H, H¹), 3.30 (d, J_HP= 5.7 Hz, 1 H,

H⁴), 3.24–3.09 (m, 1 H), 2.99–2.64 (m, 5 H), 2.39–2.13 (m, 4 H), [RuCp{η¹-(P)-PPh₂CH=C–(CH₂)₃–η³-(C,C,N)-CCHNEt₂}]PF₆

1.63–1.37 (m, 6 H) ppm. ¹³C{¹H} NMR (CD₂Cl₂, 20 °C): δ = 133.6 (4b): A stirred solution of 3b (50 mg, 0,08 mmol) in CH₃NO₂

2

(d, J_CP= 11.9 Hz, Ph^2,6), 132.2 (d, J_CP= 12.3 Hz, Ph^2Ј,6Ј), 132.2

(5 mL) was kept overnight at 80 °C. After removal of the solvent

under reduced pressure, an orange solid was obtained, which was

4

(d, J_CP= 3.3 Hz, Ph⁴), 131.4–131.6 (d, J_CP= 3.4 Hz, Ph^4Ј), 129.7

1016

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Eur. J. Inorg. Chem. 2006, 1006–1021

Reactions of Ruthenium–Aminophosphane Complexes with Diynes

FULL PAPER

washed with Et₂O (5 mL), and dried under vacuum. Yield: 45 mg

calcd. C 52.33 H 5.42, N 2.03; found C 52.25, H 5.46, N 2.12.¹H

(85%). C₂₈H₃₃F₆NP₂Ru (660.58): calcd. C 50.91, H 5.04, N 2.12;

NMR (CD₂Cl₂, 20 °C): δ = 7.96–7.79 (m, 2 H, Ph), 7.66–7.39 (m,

1

found C 50.60,; H 4.98, N 2.00. H NMR (CD₃NO₂, 20 °C): δ = 6 H, Ph), 7.34–7.18 (m, 2 H, Ph), 6.21 (d, J_HP= 9.8 Hz, 1 H, H¹),

8.08–7.88 (m, 2 H, Ph), 7.73–7.34 (m, 6 H, Ph), 7.33–7.16 (m, 2 H,

6.06 (s, 1 H, H⁴), 4.69 (s, 5 H, Cp), 3.78–3.57 (m, 1 H), 3.28–3.12

Ph), 6.35 (d, J_HP= 9.8 Hz, 1 H, H¹), 6.03 (s, 1 H, H⁴), 4.76 (s, 5

(m, 1 H), 2.72–2.40 (m, 2 H), 2.34–1.68 (m, 8 H), 1.22 (t, J_HH

=

H, Cp), 3.72–3.51 (m, 1 H), 3.03–2.44 (m, 4 H), 2.27–1.84 (m, 5 7.0 Hz, 3 H), 0.89 (t, J_HH= 7.1 Hz, 3 H) ppm. ¹³C{¹H} NMR

H), 1.21 (t, J_HH= 7.1 Hz, 3 H), 0.81 (t, J_HH= 7.1 Hz, 3 H) ppm. (CD₂Cl₂, 20 °C): δ = 169.5 (d, J_CP= 25.3 Hz, C³), 137.8 (d, J_CP

1

¹³C{¹H} NMR (CD₃NO₂, 20 °C): δ = 172.0 (d, J_CP= 27.2 Hz, C³), = 54.1 Hz, Ph¹), 134.1 (d, J_CP= 12.3 Hz, Ph^2,6), 131.8 (d, J_CP

=

2

4

1

2

1

4

137.5 (d, J_CP= 54.4 Hz, Ph¹), 134.0 (d, J_CP= 12.3 Hz, Ph^2,6),

2.3 Hz, Ph⁴), 131.1 (d, J_CP= 45.6 Hz, Ph^1Ј), 130.3 (d, J_CP

131.6 (d, ¹J_CP= 47.2 Hz, Ph^1Ј), 131.3 (d, ⁴J_CP= 2.3 Hz, Ph⁴), 130.4

2.3 Hz, Ph^4Ј), 130.3 (d, J_CP= 10.7 Hz, Ph^2Ј,6Ј), 129.0 (d, J_CP

2

3

(d, J_CP= 10.7 Hz, Ph^2Ј,6Ј), 129.9 (d, J_CP= 2.3 Hz, Ph^4Ј), 128.7

10.3 Hz, Ph^3,5), 122.5 (d, J_CP= 48.0 Hz, C¹), 90.8 (d, J_CP= 2.7 Hz,

C²), 82.7 (d, J_CP= 1.9 Hz, Cp), 79.8 (C⁴), 58.4 (CH₂), 44.9 (CH₂),

43.8 (d, J_CP= 6.5 Hz, CH₂), 36.2 (d, J_CP= 21.5 Hz, CH₂), 29.9

(CH₂), 28.3 (CH₂), 14.2 (CH₃), 12.9 (CH₃) ppm. ³¹P{¹H} NMR

2

4

(d, J_CP= 10.0 Hz, Ph^3,5), 128.6 (d, J_CP= 10.7 Hz, Ph^3Ј,5Ј), 117.4

3

(d, J_CP= 47.9 Hz, C¹), 91.3 (d, J_CP= 3.1 Hz, C²), 82.2 (d, J_CP

1.9 Hz, Cp), 79.1 (d, J_CP= 1.5 Hz, C⁴), 58.3 (CH₂), 44.1 (d, J_CP

=

8.8 Hz, CH₂), 38.4 (CH₂), 28.8 (d, J_CP= 19.6 Hz, CH₂), 25.1 (CD₂Cl₂, 20 °C): δ = 76.3 (PPh₂), –142.9 (¹J_FP= 710.8 Hz, PF₆)

(CH₂), 13.8 (CH₃), 12.1 (CH₃) ppm. ³¹P{¹H} NMR (CD₂Cl₂,

ppm.

20 °C): δ = 74.1 (PPh₂), –143.3 (¹J_FP= 707.1 Hz, PF₆) ppm.

[RuCp{η¹-(P)-PPh₂–CH=C–(CH₂)₄–η³-(C,C,N)-CH–NC₅H₁₀}]PF₆

[RuCp{η¹-(P)-PPh₂CH=C–(CH₂)₃–η³-(C,C,N)-CCHNC₅H₁₀}]PF₆(4f): This complex was prepared analogously to 4d with 1b (100 mg,

(4c): A stirred solution of 3c (50 mg, 0,07 mmol) in CH₃NO₂

(5 mL) was kept at 90 °C for 3 h. After removal of the solvent un-

der reduced pressure, an orange solid was obtained, which was

washed with Et₂O (5 mL) and dried under vacuum. Yield: 38 mg

(81%). C₂₉H₃₃F₆NP₂Ru (672.59): calcd. C 51.79, H 4.95, N 2.08;

found C 51.33, H 5.03, N 2.11. ¹H NMR (CD₃NO₂, 20 °C): δ =

8.06–7.89 (m, 2 H, Ph), 7.68–7.32 (m, 6 H, Ph), 7.30–7.14 (m, 2 H,

Ph), 6.33 (d, J_HP= 9.8 Hz, 1 H, H¹), 6.12 (1 H, H⁴), 4.73 (s, 5 H,

Cp), 3.39–3.05 (m, 2 H), 2.99–0.96 (m, 14 H) ppm. ¹³C{¹H} NMR

0.15 mmol) and 1,7-octadiyne (20.8 µL, 0.17 mmol) as starting ma-

terials. Yield: 72 mg (70 %). C₃₀H₃₅F₆NP₂Ru (686.62): calcd. C

52.48, H 5.14, N 2.04; found C 52.27, H 5.18, N 2.18. ¹H NMR

(CD₂Cl₂, 20 °C): δ = 8.00–7.77 (m, 2 H, Ph), 7.72–7.36 (m, 6 H,

2

Ph), 7.33–7.14 (m, 2 H, Ph), 6.18 (d, J_HP= 9.5 Hz, 1 H, H¹), 6.14

(1 H, H⁴), 4.68 (s, 5 H, Cp), 3.41–3.07 (m, 3 H), 2.66–2.40 (m, 1

H), 2.38–1.51 (m, 11 H), 1.43–0.99 (m, 3 H) ppm. ¹³C{¹H} NMR

1

(CD₂Cl₂, 20 °C): δ = 169.3 (d, J_CP= 25.7 Hz, C³), 138.1 (d, J_CP

2

4

= 53.7 Hz, Ph¹), 134.2 (d, J_CP= 12.3 Hz, Ph^2,6), 131.7 (d, J_CP

=

(CD₃NO₂, 20 °C): δ = 171.7 (d, J_CP= 28.0 Hz, C³), 137.8 (d, J_CP

2.3 Hz, Ph⁴), 131.3 (d, J_CP= 45.6 Hz, Ph^1Ј), 130.2 (d, J_CP

1

2

1

4

3

= 54.1 Hz, Ph¹), 134.1 (d, J_CP= 11.9 Hz, Ph^2,6), 131.9 (d, J_CP

=

11.1 Hz, Ph^2Ј,6Ј), 130.1 (d, J_CP= 2.3 Hz, Ph^4Ј), 129.2 (d, J_CP

4

2

3

44.9 Hz, Ph^1Ј), 131.2 (d, J_CP= 2.3 Hz, Ph⁴), 130.3 (d, J_CP

10.0 Hz, Ph^3,5), 128.9 (d, J_CP= 10.7 Hz, Ph^3Ј,5Ј), 122.2 (d, J_CP

4

3

10.7 Hz, Ph^2Ј,6Ј), 129.8 (d, J_CP= 2.3 Hz, Ph^4Ј), 128.9 (d, J_CP

47.5 Hz, C¹), 91.0 (d, J_CP= 2.7 Hz, C²), 82.7 (d, J_CP= 1.9 Hz, Cp),

77.2 (C⁴), 68.7 (CH₂), 44.6 (CH₂), 36.5 (d, J_CP= 21.5 Hz, CH₂),

30.0 (CH₂), 28.3 (CH₂), 27.9 (CH₂), 27.4 (CH₂), 22.7 (CH₂) ppm.

3

10.0 Hz, Ph^3,5), 128.6 (d, J_CP= 10.4 Hz, Ph^3Ј,5Ј), 117.3 (d, J_CP

47.9 Hz, C¹), 91.5 (d, J_CP= 3.1 Hz, C²), 82.3 (d, J_CP= 1.9 Hz, Cp),

79.0 (C⁴), 68.0 (CH₂), 52.6 (d, J_CP= 7.7 Hz, CH₂), 38.1 (CH₂), ³¹P{¹H} NMR (CD₂Cl₂, 20 °C): δ = 76.2 (PPh₂), –142.9 (¹J_FP

=

28.9 (d, J_CP= 19.9 Hz, CH₂), 27.3 (CH₂), 24.8 (d, J_CP= 1.5 Hz, 710.8 Hz, PF₆) ppm.

CH₂), 22.3 (CH₂) ppm. ³¹P{¹H} NMR (CD₃NO₂, 20 °C): δ = 73.3

[RuCp{=C(NEt₂)-η²-(C,C)-C–(CH₂)₃–CCH₂-(η¹-(P)-PPh₂)}]PF₆

(5a): A solution of 4b (96 mg, 0.15 mmol) in acetonitrile was heated

(PPh₂), –143.2 (¹J_FP= 707.1 Hz, PF₆) ppm.

[RuCp{η¹-(P)-PPh₂–CH=C–(CH₂)₄–η³-(C,C,N)-CH–NnPr}]PF₆at 90 °C for 12 h. After removal of the solvent under reduced pres-

(4d): 1.1 equiv. of 1,7-octadiyne (21.9 µL, 0.17 mmol) was added to

sure, an orange solid was obtained, which was washed with Et₂O

a solution of 1a (100 mg, 0.16 mmol) in CH₂Cl₂(10 mL) and the (5 mL) and dried under vacuum. Yield: 70 mg (71 %).

mixture was heated for 8 h at 40 °C. After removal of the solvent

under reduced pressure, an orange solid was obtained, which was

washed with Et₂O (5 mL) and dried under vacuum. Yield: 82 mg

(78%). C₂₉H₃₅F₆NP₂Ru (674.61): calcd. C 51.63, H 5.23, N 2.08;

C₂₉H₃₅F₆NP₂Ru (688.64): calcd. C 52.33, H 5.42, N 2.03; found C

52.57, H 5.27, N 2.11. ¹H NMR (CD₃CN, 20 °C): δ = 7.68–7.31

(m, 10 H, Ph), 4.95 (s, 5 H, Cp), 4.06–3.79 (m, 3 H, CH₂, H¹),

3.77–3.47 (m, 3 H, CH₂, H^1Ј), 2.82–2.55 (m, 2 H), 2.27–2.07 (m, 1

found C 51.60, H 5.11, N 2.04. ¹H NMR (CD₂Cl₂, 20 °C): δ = H), 2.03–1.74 (m, 2 H), 1.58–1.35 (m, 1 H), 1.12 (t, J_HH= 7.3 Hz,

7.92–7.76 (m, 2 H, Ph), 7.68–7.40 (m, 6 H, Ph), 7.37–7.20 (m, 2 H,

3 H), 0.84 (t, J_HH= 7.3 Hz, 3 H) ppm. ¹³C{¹H} NMR (CD₃CN,

2

1

Ph), 6.17 (d, J_HP= 7.1 Hz, 1 H, H⁴), 5.95 (d, J_HP= 10.1 Hz, 1 H,

20 °C): δ = 225.2 (d, J_CP= 13.0 Hz, C⁴), 137.5 (d, J_CP= 46.8 Hz,

H¹), 4.78 (s, 5 H, Cp), 3.16–2.88 (m, 2 H), 2.84–2.62 (m, 1 H), Ph¹), 132.4 (d, J_CP= 12.3 Hz, Ph^2,6), 131.3 (d, J_CP= 36.0 Hz,

2

1

2

4

2.47–2.07 (m, 4 H), 1.94–1.61 (m, 2 H), 1.57–1.23 (m, 3 H), 0.72

Ph^1Ј), 131.0 (d, J_CP= 11.5 Hz, Ph^2Ј,6Ј), 130.9 (d, J_CP= 3.1 Hz,

(t, J_HH= 7.4 Hz, 3 H) ppm. ¹³C{¹H} NMR (CD₂Cl₂, 20 °C): δ =

Ph⁴), 130.4 (d, J_CP= 3.1 Hz, Ph^4Ј), 128.9 (d, J_CP= 10.7 Hz,

4

3

1

3

165.8 (d, J_CP= 26.5 Hz, C³), 136.5 (d, J_CP= 52.5 Hz, Ph¹), 134.1

Ph^3,5), 128.6 (d, J_CP= 10.7 Hz, Ph^3Ј,5Ј), 83.3 (Cp), 73.8 (d, J_CP

=

2

4

(d, J_CP= 11.9 Hz, Ph^2,6), 131.8 (d, J_CP= 2.3 Hz, Ph⁴), 130.9 (d, 16.1 Hz, C²), 71.7 (d, J_CP= 3.1 Hz, C³), 51.7 (d, J_CP= 26.8 Hz,

¹J_CP= 48.7 Hz, Ph^1Ј), 130.4 (d, ⁴J_CP= 2.3 Hz, Ph^4Ј), 130.3 (d, ²J_CP

CH₂), 37.7 (d, J_CP= 7.7 Hz, CH₂), 37.0 (d, J_CP= 35.3 Hz, CH₂,

C¹), 32.7 (CH₂), 22.5 (CH₂), 13.2 (CH₃), 12.4 (CH₃) ppm. ³¹P{¹H}

NMR (CD₃CN, 20 °C): δ = –34.3 (PPh₂), –143.1 (¹J_FP= 706.8 Hz,

= 11.5 Hz, Ph^2Ј,6Ј), 129.2 (d, J_CP= 10.4 Hz, Ph^3,5), 129.0 (d, J_CP

3

= 10.7 Hz, Ph^3Ј,5Ј), 119.9 (d, J_CP= 46.0 Hz, C¹), 84.2 (d, J_CP

=

1.9 Hz, C²), 81.8 (d, J_CP= 1.9 Hz, Cp), 72.0 (C⁴), 57.6 (CH₂), 41.1 PF₆) ppm.

(CH₂), 35.7 (d, J_CP= 20.3 Hz, CH₂), 29.1 (CH₂), 27.7 (CH₂), 24.7

Isomerization of 3c to 4c and [RuCp{=C(NC₅H₁₀)-η²-(C,C)-C–

(CH₂), 10.4 (CH₃) ppm.

(CH₂)₃–CCH₂-(η¹-(P)-PPh₂)}]PF₆(5b): A 5-mm NMR tube was

charged with 3c (30 mg, 0.04 mmol) in CD₃CN (0.5 mL) and

heated to 90 °C. The reaction was then monitored by ¹H and

³¹P{¹H} NMR spectroscopy. After 48 h both 4c and 5b were

formed in an approximately 3:1 ratio. Because of spectral overlap

[RuCp{η¹-(P)-PPh₂–CH=C–(CH₂)₄–η³-(C,C,N)-CH–NEt₂}]PF₆

(4e): This complex was prepared analogously to 4d with 1b

(100 mg, 0.15 mmol) and 1,7-octadiyne (20.8 µL, 0.17 mmol) as

starting materials. Yield: 56 mg (55%). C₃₀H₃₇F₆NP₂Ru (688.64):

Eur. J. Inorg. Chem. 2006, 1006–1021

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1017

S. Pavlik, F. Jantscher, G. Dazinger, K. Mereiter, K. Kirchner

FULL PAPER

with 4c only the most characteristic signals of 5b could be unequiv-

ocally assigned. H NMR (CD₃CN, 20 °C): δ = 4.93 (s, 5 H, Cp),

solution was then reduced to about 1 mL. Addition of 5 mL of

Et₂O resulted in the formation of a yellow precipitate, which was

1

3.66–3.49 (m, 2 H, H¹) ppm. ¹³C{¹H} NMR (CD₃CN, 20 °C): δ = washed with Et₂O (2 × 5 mL) and dried under vacuum. Yield:

222.9 (d, J_CP= 12.3 Hz, C⁴), 83.2 (Cp), 74.3 (d, J_CP= 16.9 Hz, 83 mg (82%). C₃₄H₄₃F₆NP₂Ru (742.73): calcd. C 54.98, H 5.84, N

C²), 71.2 (C³), 36.7 (d, J_CP= 35.3 Hz, CH₂, C¹) ppm. ³¹P{¹H} 1.89; found C 54.84, H 5.76, N 1.93. H NMR (CD₂Cl₂, 20 °C): δ

1

NMR (CD₃CN, 20 °C): δ = –37.8 (PPh₂), –144.6 (¹J_FP= 707.7 Hz, = 7.76–6.99 (m, 10 H, Ph), 6.05 (d, J_HP= 8.7 Hz, 1 H, H¹), 5.07

PF₆) ppm.

(s, 1 H, H⁴), 3.23–2.92 (m, 2 H), 2.88–2.69 (m, 2 H), 2.66–2.43 (m,

2 H), 2.41–1.92 (m, 3 H), 1.91–1.53 (m, 3 H), 1.48 (s, 15 H, Cp*),

1.35–1.01 (m, 4 H) ppm. ¹³C{¹H} NMR (CD₂Cl₂, 20 °C): δ = 169.8

[RuCp*{η¹-(N)-NnPrPPh₂–η⁴-CH=C–(CH₂)₃–C=CH₂}]PF₆(6a):

1 equiv. of 1,6-heptadiyne (16 µL, 0.14 mmol) was added to a solu-

tion of 2a (100 mg, 0.14 mmol) in CH₂Cl₂(5 mL) and the mixture

was stirred for 2 h at room temperature. After that the volume of

the solution was reduced to about 1 mL and Et₂O (5 mL) was

added whereupon a precipitate was formed. The yellow solid was

washed with Et₂O (2 × 5 mL) and dried under vacuum. Yield:

68 mg (68%). C₃₂H₄₁F₆NP₂Ru (716.69): calcd. C 53.63, H 5.77, N

1

(d, J_CP= 28.4 Hz, C³), 134.1 (d, J_CP= 49.8 Hz, Ph¹), 132.3 (d,

1

²J_CP= 10.7 Hz, Ph^2,6,2Ј,6Ј), 131.6 (Ph⁴), 131.5 (d, J_CP= 40.6 Hz,

3

Ph^1Ј), 130.3 (C^4Ј), 129.2 (d, J_CP= 9.2 Hz, Ph^3,5), 128.7 (d, J_CP

=

9.2 Hz, Ph^3Ј,5Ј), 119.7 (d, J_CP= 46.0 Hz, C¹), 92.8 (Cp*), 91.4 (d,

1

J_CP= 3.1 Hz, C²), 85.9 (C⁴), 64.7 (CH₂), 51.4 (d, J_CP= 6.9 Hz,

CH₂), 36.5 (CH₂), 29.1 (d, J_CP= 19.2 Hz, CH₂), 27.7 (d, J_CP

=

17.6 Hz, CH₂), 25.7 (CH₂), 22.8 (CH₂), 9.6 (Cp*) ppm. ³¹P{¹H}

NMR (CD₂Cl₂, 20 °C): δ = 68.7 (PPh₂), –144.4 (¹J_FP= 710.8 Hz,

PF₆) ppm.

1

1.95; found C 54.01, H 5.56, N 2.06. H NMR (CD₂Cl₂, 20 °C): δ

= 7.78–7.32 (m, 10 H, Ph), 3.88 (d, J_HH= 3.5 Hz, 1 H, H⁴), 3.52–

2

3.31 (m, 2 H), 3.18 (d, J_HP= 16.3 Hz, 1 H, H¹), 2.64 (d, J_HH

=

3.3 Hz, 1 H, H^4Ј), 2.56–2.40 (m, 1 H), 2.39–2.28 (m, 2 H), 2.27–

2.06 (m, 3 H), 1.67 (s, 15 H, Cp*), 1.34–1.20 (m, 2 H), 0.70 (t, J_HH

= 7.3 Hz, 3 H) ppm. ¹³C{¹H} NMR (CD₂Cl₂, 20 °C): δ = 133.5–

128.5 (Ph), 119.1 (C²), 112.5 (C³), 98.1 (Cp*), 50.4 (CH₂), 46.7

(C⁴), 37.0 (d, J_CP= 7.7 Hz, CH₂), 35.3 (CH₂), 29.8 (CH₂), 22.0 (d,

J_CP= 112.7 Hz, C¹), 20.5 (CH₂), 11.2 (CH₃), 9.2 (Cp*) ppm.

[RuCp*{η¹-(P)-PPh₂CH=C–(CH₂)₄–η³-(C,C,N)-C=CH–NEt₂}]PF₆

(8c): This complex was prepared analogously to 8b with 2b

(100 mg, 0.14 mmol) and 1,7-octadiyne (16 µL, 0.14 mmol) as the

starting materials. Yield: 75 mg (72%). C₃₄H₄₅F₆NP₂Ru (744.74):

1

calcd. C 54.83, H 6.09, N 1.88; found C 54.62, H 6.19, N 1.98. H

2

NMR (CD₂Cl₂, 20 °C): δ = 7.90–7.10 (m, 10 H, Ph), 6.08 (d, J_HP

³¹P{¹H} NMR (CD₂Cl₂, 20 °C): δ = 47.5 (PPh₂), –144.4 (¹J_FP

=

= 8.5 Hz, 1 H, H¹), 5.22 (s, 1 H, H⁴), 3.58 (m, 1 H), 3.16 (m, 1

HЈ), 2.59 (m, 1 H), 2.27–1.94 (m, 5 H), 1.93–1.53 (m, 4 H), 1.46

(d, J_HP= 1.8 Hz 15 H, Cp*), 1.16 (t, J_HH= 7.2 Hz, 3 H, CH₃),

0.84 (t, J_HH= 7.2 Hz, 3 H, CH₃) ppm. ¹³C{¹H} NMR (CD₂Cl₂,

710.8 Hz, PF₆) ppm.

[RuCp*{η¹-(N)-NnPrPPh₂–η⁴-CH=C–(CH₂)₄–C=CH₂}]PF₆(6b):

This complex was prepared analogously to 6a with 2a (100 mg,

0.14 mmol) and 1,7-octadiyne (19 µL, 0.14 mmol) as the starting

materials. Yield: 64 mg (63%). C₃₃H₄₃F₆NP₂Ru (730.72): calcd. C

54.24, H 5.93, N 1.29; found C 54.35, H 5.88, N 1.22. ¹H NMR

1

20 °C): δ = 167.1 (d, J_CP= 26.8 Hz, C³), 134.6 (d, J_CP= 49.8 Hz,

Ph¹), 132.5 (d, ²J_CP= 10.7 Hz, Ph^2,6,2Ј,6Ј), 131.7 (d, ¹J_CP= 41.4 Hz,

Ph^1Ј), 131.6 (d, J_CP= 2.3 Hz, Ph⁴), 130.4 (d, J_CP= 3.1 Hz, Ph^4Ј),

128.9 (d, J_CP= 9.2 Hz, Ph^3,5), 128.7 (d, J_CP= 10.0 Hz, Ph^3Ј,5Ј),

126.1 (d, J_CP= 46.8 Hz, C¹), 92.9 (Cp*), 88.9 (d, J_CP= 3.1 Hz,

C²), 88.1 (C⁴), 55.7 (CH₂), 42.0 (CH₂), 41.7 (d, J_CP= 6.1 Hz, CH₂),

35.9 (d, J_CP= 20.7 Hz, CH₂), 29.6 (CH₂), 27.9 (CH₂), 12.8 (CH₃),

12.6 (CH₃), 9.2 (Cp*) ppm. ³¹P{¹H} NMR (CD₂Cl₂, 20 °C): δ =

70.5 (PPh₂), –144.4 (¹J_FP= 710.5 Hz, PF₆) ppm.

(CD₂Cl₂, 20 °C): δ = 7.78–7.26 (m, 10 H, Ph), 3.70 (d, J_HH

=

3.5 Hz, 1 H, H⁴), 3.15–2.87 (m, 2 H), 2.76 (d, J_HP= 13.6 Hz, 1

H, H¹), 2.61–2.28 (m, 2 H), 2.43 (d, J_HH= 3.8 Hz, 1 H, H^4Ј), 1.90–

1.72 (m, 4 H), 1.69 (s, 15 H, Cp*), 1.59–1.49 (m, 4 H), 0.74 (t, J_HH

= 7.3 Hz, 3 H) ppm. ¹³C{¹H} NMR (CD₂Cl₂, 20 °C): δ = 135.9–

126.9 (Ph), 113.3 (C²), 105.4 (C³), 99.1 (Cp*), 51.3 (d, J_CP= 3.1 Hz,

CH₂), 48.6 (C⁴), 30.7 (d, J_CP= 8.4 Hz, CH₂), 30.4 (CH₂), 29.7

(CH₂), 23.5 (d, J_CP= 108.1 Hz, C¹), 21.7 (d, J_CP= 1.2 Hz, CH₂),

21.4 (CH₂), 11.2 (CH₂), 9.5 (Cp*) ppm. ³¹P{¹H} NMR (CD₂Cl₂,

20 °C): δ = 55.7 (PPh₂), –142.9 (¹J_FP= 710.8 Hz, PF₆) ppm.

2

[RuCp*{η¹-(P)-PPh₂CH=C–(CH₂)₄–η³-(C,C,N)-C=CH–N-

(CH₂)₅}]PF₆(8d): This complex was prepared analogously to 8b

with 2c (100 mg, 0.14 mmol) and 1,7-octadiyne (19 µL, 0.14 mmol)

as the starting materials. Yield: 80 mg (77 %). C₃₅H₄₅F₆NP₂Ru

(756.75): calcd. C 55.55, H 5.99, N 1.85; found C 56.00, H 5.89, N

1.69. ¹H NMR (CD₂Cl₂, 20 °C): δ = 7.77–7.32 (m, 10 H, Ph), 6.02

(d, J_HP= 8.5 Hz, 1 H, H¹), 5.17 (s, 1 H, H⁴), 3.18–2.90 (m, 4 H),

2.48–2.20 (m, 2 H), 2.19–2.96 (m, 4 H), 1.90–1.50 (m, 6 H), 1.45

(d, J_HP= 1.7 Hz, 15 H, Cp*), 1.39–1.24 (m, 2 H) ppm. ¹³C{¹H}

NMR (CD₂Cl₂, 20 °C): δ = 166.4 (d, J_CP= 26.1 Hz, C³), 134.7 (d,

Reaction of 2b with 1,6-Heptadiyne in CD₂Cl₂. Formation of

[RuCp*{η³-(P,C,C)–PPh₂–CH–C(CH₂)₄–η²-(C,C)-CCHNEt₂}]PF₆

(7) and [RuCp*{η¹-(P)-PPh₂–CH=C–(CH₂)₃–η³-(C,C,N)-

CCHNEt₂}]PF₆(8a): A 5-mm NMR tube was charged with 2b

(56 mg, 0.08 mmol) in CD₂Cl₂(0.5 mL) and 1,6-heptadiyne

(8.9 µL, 0.08 mmol) was added by syringe. The reaction was then

monitored by ¹H and ³¹P{¹H} NMR spectroscopy. After 10 min

both 7 and 8a were formed in an approximately 1:1 ratio. Because

of spectral overlap with one another only the most characteristic

2

¹J_CP= 49.8 Hz, Ph¹), 132.6 (d, J_CP= 10.0 Hz, Ph^2,6), 132.2 (d,

²J_CP= 9.2 Hz, Ph^2Ј,6Ј), 131.6 (Ph⁴), 131.6 (d, ¹J_CP= 48.3 Hz, Ph^1Ј),

3

130.4 (C^4Ј), 129.1 (d, J_CP= 10.0 Hz, Ph^3,5), 128.7 (d, J_CP

=

10.0 Hz, Ph^3Ј,5Ј), 126.2 (d, J_CP= 46.0 Hz, C¹), 92.8 (Cp*), 89.5

(C²), 84.4 (C⁴), 65.2 (CH₂), 52.6 (d, J_CP= 4.6 Hz, CH₂), 45.8

(CH₂), 41.8 (CH₂), 36.1 (d, J_CP= 20.7 Hz, CH₂), 29.7 (CH₂), 28.0

(d, J_CP= 17.6 Hz, CH₂), 27.9 (CH₂), 23.0 (CH₂), 9.7 (Cp*) ppm.

1

signals of 7 and 8a could be unequivocally assigned. 7: H NMR

2

(CD₂Cl₂, 20 °C): δ = 4.17 (d, J_HP= 4.3 Hz, 1 H, H¹), 3.7 (d, J_HP

= 4.4 Hz, 1 H, H⁴), 1.67 (d, J_HP= 1.9 Hz, 15 H, Cp*) ppm.

¹³C{¹H} NMR (CD₂Cl₂, 20 °C): δ = –10.0 (PPh₂), –144.4 (¹J_FP

=

³¹P{¹H} NMR (CD₂Cl₂, 20 °C): δ = 72.2 (PPh₂), –144.4 (¹J_FP

=

1

2

710.2 Hz, PF₆). 8a: H NMR (CD₂Cl₂, 20 °C): δ = 6.08 (d, J_HP

8.4 Hz, 1 H, H¹), 5.17 (s, 1 H, H⁴), 1.48 (d, J_HP= 1.6 Hz, 15 H,

Cp*) ppm. ³¹P{¹H} NMR (CD₂Cl₂, 20 °C): δ = 67.8 (PPh₂), –144.4

(¹J_FP= 710.2 Hz, PF₆) ppm.

710.8 Hz, PF₆) ppm.

Formation of [RuCp{κ¹(P)-PPh₂NHNMe₂}(CH₃CN)₂]PF₆(9) and

[RuCp{κ²(P,N)-PPh₂NHNMe₂} (CH₃CN)]PF₆(10): PPh₂NHNMe₂

[RuCp*{η¹-(P)-PPh₂CH=C–(CH₂)₃–η³-(C,C,N)-C=CH–N- (188 mg, 0.77 mmol) was added to a solution of [RuCp(CH₃CN)₃]-

(CH₂)₅}]PF₆(8b): 1,6-Heptadiyne (16 µL, 0.14 mol) was added to

a solution of 2c (100 mg, 0.14 mmol) in CH₂Cl₂(5 mL) and the stirred for 2 h at room temperature. The volume of the solution

mixture was stirred for 2 h at room temperature. The volume of the was then reduced to about 1 mL and Et₂O (5 mL) was added. A

PF₆(335 mg, 0.77 mmol) in CH₂Cl₂(5 mL) and the mixture was

1018

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Eur. J. Inorg. Chem. 2006, 1006–1021

Reactions of Ruthenium–Aminophosphane Complexes with Diynes

FULL PAPER

yellow precipitate was formed, which was collected on a glass frit,

washed with Et₂O (3×10 mL), and dried under vacuum. ¹H NMR

spectroscopy revealed that 9 and 10 were formed in an approxi-

mately 5:1 ratio. If the same reaction was performed in the presence

of acetonitrile (40 µL, 0.77 mmol), complex 9 was exclusively ob-

tained. Yield: 398 mg (84%). C₂₃H₂₈F₆N₄P₂Ru (637.51): calcd. C

ture refinement on F²was carried out with the program

SHELXL97.^[24]All non-hydrogen atoms were refined anisotropi-

cally. Hydrogen atoms were inserted in idealized positions and were

refined riding with the atoms to which they were bonded, except

for N-bound hydrogen atoms, which were refined in x,y,z if permit-

ted by data quality.^[26]Compound 6b crystallizes in the acentric

43.33, H 4.43, N 8.79; found C 42.98; H 4.50, N 8.61. ¹H NMR triclinic space group P1 (no. 1) with three independent Ru com-

(CD₂Cl₂, 20 °C): δ = 7.74–7.54 (m, 4 H, Ph), 7.53–7.39 (m, 6 H, plexes in the unit cell. Two of these three complexes adopt a pseu-

2

¯

Ph), 4.45 (s, 5 H, Cp), 3.51 (d, J_HP= 34.1 Hz, 1 H, NH), 2.27 (6 docentric arrangement (pseudo space group P1) while the third

H, CH₃), 2.26 (d, J_HP= 1.3 Hz, 6 H, CH₃CN) ppm. ¹³C{¹H} NMR

complex does not comply with this symmetry. In Figure 8 only the

(CD₂Cl₂, 20 °C): δ = 136.2 (d, J_CP= 51.7 Hz, Ph¹), 132.6 (d, J_CPfirst of these three complexes is shown as a representative example.

1

2

4

3

= 12.1 Hz, Ph^2,6), 130.2 (d, J_CP= 2.3 Hz, Ph⁴), 127.9 (d, J_CP

=

CCDC-286740 to -286750 contain the supplementary crystallo-

graphic data for this paper. These data can be obtained free of

charge from The Cambridge Crystallographic Data Centre via

www.ccdc.cam.ac.uk/data_request/cif.

9.8 Hz, Ph^3,5), 127.0 (CH₃CN), 76.4 (d, J_CP= 2.9 Hz, Cp), 49.9 (d,

J_CP= 3.4 Hz, CH₃) 3.8 (d, J_CP= 1.2 Hz, CH₃CN) ppm. ³¹P{¹H}

NMR (CD₂Cl₂, 20 °C): δ = 90.6 (PPh₂), –142.9 (¹J_FP= 710.8 Hz,

PF₆) ppm. All attempts to grow crystals of 9 were unsuccessful.

Crystals of 10 were grown by diffusion of diethyl ether into a

CH₂Cl₂solution of the reaction mixture containing 9 and 10. 10:

¹H NMR (CD₂Cl₂, 20 °C): δ = 7.72–7.36 (m, 10 H, Ph), 4.48 (s, 5

H, Cp), 3.35 (s, 3 H, Me), 2.82 (s, 3 H, Me), 2.14 (d, J_HP= 1.6 Hz,

CH₃CN) ppm. The NH proton could not be detected. ¹³C{¹H}

NMR (CD₂Cl₂, 20 °C): δ = 132.9–128.5 (Ph), 128.1 (CH₃CN), 73.0

(Cp), 63.9 (CH₃), 57.8 (CH₃), 3.85 (CH₃CN) ppm. ³¹P{¹H} NMR

(CD₂Cl₂, 20 °C): δ = 61.4 (PPh₂), –142.9 (¹J_FP= 711.5 Hz, PF₆)

ppm.

Computational Details: All calculations were performed using the

Gaussian98 software package on the Silicon Graphics Origin 2000

of the Vienna University of Technology.^[27]The geometry and en-

ergy of the model complexes and the transition states were opti-

mized at the B3LYP level^[28]with the Stuttgart/Dresden ECP

(SDD) basis set^[29]to describe the electrons of the ruthenium atom.

For the C, N, P, and H atoms the 6-31g** basis set was em-

ployed.^[30]A vibrational analysis was performed to confirm that the

structures of the model compounds have no imaginary frequency.

Transition state optimizations were performed with the Synchro-

nous Transit-Guided Quasi-Newton Method (STQN) developed by

Schlegel et al.^[31]Frequency calculations were performed to confirm

the nature of the stationary points, yielding one imaginary fre-

quency for the transition states and none for the minima. The vi-

brational eigenvectors corresponding to the reaction coordinate

(with imaginary frequency) of all transition states were visually

checked to confirm the connectivity of transition states with the

reactants and the products. Crucial transition states have been con-

firmed by IRC calculations. All geometries were optimized without

symmetry constraints.

X-ray Structure Determination: Crystals of 1a, 2a, 3c, 3f, 4a, 5a,

6a, 6b, 8c·CH₂Cl₂, 8d, and 10 were obtained by diffusion of Et₂O

or pentane into CH₂Cl₂solutions. Crystal data and experimental

details are given in Table 1 and Table 2. X-ray data were collected

with a Bruker Smart APEX CCD area detector diffractometer

using graphite-monochromated Mo-K_αradiation (λ = 0.71073 Å)

and 0.3° ω-scan frames covering mostly complete spheres of the

reciprocal space. Corrections for absorption (multi-scan method),

λ/2 effects, and crystal decay were applied.^[24]The structures were

solved by direct methods using the program SHELXS97.^[25]Struc-

Table 2. Details for the crystal structure determinations of complexes 6a, 6b, 8c·CH₂Cl₂, 8d, and 10.

6a

6b

8c·CH₂Cl₂

8d

10

Empirical formula

Formula mass

Crystal size [mm]

Space group

a [Å]

b [Å]

c [Å]

C₃₂H₄₁F₆NP₂Ru

716.67

0.48×0.26×0.22

P2₁2₁2₁(no. 19)

9.8943(4)

16.3485(7)

19.3928(8)

90

3136.9(2)

4

1.517

173(2)

0.661

1472

C₃₃H₄₃F₆NP₂Ru

730.69

C₃₅H₄₇Cl₂F₆NP₂Ru C₃₅H₄₅F₆NP₂Ru

C₂₁H₂₅F₆N₃P₂Ru

596.45

829.65

0.56×0.48×0.42

Pna2₁(no. 33)

17.2512(7)

13.7579(6)

15.7043(7)

90

756.73

0.40×0.27×0.17

Pbca (no. 61)

18.9953(9)

18.2714(8)

19.2964(9)

90

0.71×0.32×0.22

P1 (no. 1)

10.9184(5)

12.1773(5)

20.3660(8)

96.037(1)

103.790(1)

109.460(1)

2428.6(2)

3

1.499

173(2)

0.642

1128

0.62×0.33×0.26

P2₁2₁2₁(no. 19)

7.9113(49)

15.3880(8)

19.3607(10)

90

2357.0(2)

4

1.681

α [°]

β [°]

90

γ [°]

90

3727.3(3)

4

90

6697.2(5)

8

V [Å³]

Z

ρ_calcd[g/cm³]

T [K]

1.478

173(2)

0.706

1.501

173(2)

0.623

173(2)

0.863

1200

µ [mm^–1] (Mo-K_α)

F(000)

1704

3120

θ_max[°]

Measured reflections

Unique reflections

30

35175

9048

30

45589

28007

30

80284

10830

30

96310

9743

30

35290

6675

No. of reflections I Ͼ 2σ(I) 8633

27374

1202

0.0271

0.0279

0.0714

–0.42/0.94

10223

435

0.0288

0.0325

0.0807

–0.77/1.01

7562

417

0.0325

0.0505

0.0765

–0.34/0.46

6858

302

0.0211

0.0219

0.0540

–0.44/0.46

Parameters

385

R₁[I Ͼ 2σ(I)]^[a]

R₁(all data)

0.0313

0.0335

0.0846

–0.34/0.80

wR₂(all data)

∆ρ_min/max[e/Å³]

2 2

[a] R₁= Σ||F_o| – |F_c||/Σ|F_o|, wR₂= {Σ[w(F_o²–F_c) ]/Σ[w(F_o²)²]}^1/2

.

Eur. J. Inorg. Chem. 2006, 1006–1021

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Received: October 25, 2005

Published Online: January 16, 2006

Eur. J. Inorg. Chem. 2006, 1006–1021

www.eurjic.org

1021

Article Doi

Reactions of ruthenium-aminophosphane complexes with diynes: P-N bond activation and formation of novel phosphaallyl, azaallyl, and aminocarbene complexes

DOI: 10.1002/ejic.200500942

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Authors:

Article abstract of DOI:10.1002/ejic.200500942

Full text of DOI:10.1002/ejic.200500942

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