Reactions of the cationic fragments [RuCp(PPh2NHR) 2]+ and [RuTp(PPh2NHR)2]+ (R = Ph, re-Pr) with Alkynes: Formation of four-membered azaphosphacarbenes

Organometallics 2005, 24, 3561-3575

3561

Reactions of the Cationic Fragments

[RuCp(PPh₂NHR)₂]⁺and [RuTp(PPh₂NHR)₂]⁺(R ) Ph,

n-Pr) with Alkynes: Formation of Four-Membered

Azaphosphacarbenes

Sonja Pavlik,^†Kurt Mereiter,^‡Michael Puchberger,^‡and Karl Kirchner*^,†

Institute of Applied Synthetic Chemistry, Institute of Chemical Technologies and Analytics,

and Institute of Materials Chemistry, Vienna University of Technology, Getreidemarkt 9,

A-1060 Vienna, Austria

Received April 2, 2005

The synthesis of RuCp(PPh₂NHR)₂Cl (1a,b; R ) Ph, n-Pr) and RuTp(PPh₂NHR)₂Cl (2a,b)

is reported. Chloride abstraction from 1a with AgCF₃SO₃affords RuCp(PPh₂NHPh)₂(η¹-

OSO₂CF₃) (3), whereas when AgSbF₆is used instead [RuCp(κ²(P,P)-PPh₂NHC₆H₄PPh₂)(NH₂-

Ph)]⁺(4) is formed. In the course of this reaction the P-N bond of one PPh₂NHPh ligand is

cleaved while a new P-C bond is formed, with concomitant formation of an aniline ligand.

-

In the presence of Ag⁺(CF₃SO₃or SbF₆) complexes 1 and 2 react with terminal alkynes

HCtCR′ (R′ ) Ph, p-C₆H₄Me, n-Bu) and propargylic alcohols to give novel azaphosphacarbene

complexes of the types [RuCp(κ²(C,P)dC(CH₂R′)N(R)PPh₂)(κ¹(P)-PPh₂NHR)]⁺(5a-c, 6a-

c), [RuTp(κ²(C,P)dC(CH₂R′)N(R)PPh₂)(κ¹(P)-PPh₂NHR)]⁺(14a,b, 15a-c), [RuCp(κ²(C,P)d

C(CHdCPh₂)N(Prⁿ)PPh₂)(κ¹(P)-PPh₂NHPrⁿ)]⁺(12), and [RuTp(κ²(C,P)dC(CHdCPh₂)N(Prⁿ)-

PPh₂)(κ¹(P)-PPh₂NHPrⁿ)]⁺(17). These reactions proceed via vinylidene and allenylidene

intermediates, respectively, which could be isolated in some cases: viz. [CpRu(PPh₂NHPh)₂-

(dCdCdCPh₂)]⁺(11) and [RuTp(PPh₂NHR)₂(dCdCdCPh₂)]⁺(16a,b). Furthermore, com-

plexes 1a,b react with 3-butyn-1-ol to yield the oxacyclopentylidene complexes [CpRu(PPh₂-

NHR)₂(dC₄H₆O)]⁺(7a,b). In sharp contrast to 6a-c (R ) n-Bu), 5a-c (R ) Ph) turned out

to be quite sensitive toward traces of water, leading eventually to the formation of the

aminocarbene complexes [RuCp(dC(CH₂R)NHPh)(PPh₂NHPh)(κ¹(P)-PPh₂OH)]⁺(8a,b) fea-

turing a κ¹(P)-coordinated PPh₂OH ligand. This ligand could be easily deprotonated to yield

the neutral complex RuCp(dC(CH₂Ph)NHR)(PPh₂NHPh)(κ¹(P)-OPPh₂) (10a,b). The forma-

tion of these complexes is reversible. Finally, representative structures have been determined

by X-ray crystallography.

Introduction

stabilized carbene complexes become readily available.

Such reactions have been shown to be particularly facile

in the intramolecular mode⁶through utilizing bifunc-

Ruthenium vinylidene and allenylidene complexes

play an important role in organometallic chemistry, as

emphasized in several recent reviews.¹Interest in these

compounds stems from the fact that they are intermedi-

ates in several stoichiometric and catalytic transforma-

tions of organic molecules. Moreover, they are readily

accessible from terminal alkynes and propargylic alco-

hols. A key characteristic of all these complexes, par-

ticularly if they are cationic, is the electrophilicity of

the R-carbon, adding, often easily, amines,²alcohols,³

phosphines,⁴and even fluoride.⁵In this way heteroatom-

(2) (a) Bernad, D. J.; Esteruelas, M. A.; Lopez, A. M.; Modrego, J.;

Puerta, M. C.; Valerga, P. Organometallics 1999, 18, 4995. (b)

Bianchini, C.; Casares, J. A.; Peruzzini, M.; Romerosa, A.; Zanobini,

F. J. Am. Chem. Soc. 1996, 118, 4585. (c) Barrett, G. M.; Carpenter,

N. E. Organometallics 1987, 6, 2249. (d) Ouzzine, K.; Le Bozec, H.;

Dixneuf, P. H. J. Organomet. Chem. 1986, 317, C25. (e) Gamasa, M.

P.; Gimeno, J.; Gonzaleszcueva, M.; Lastra, E. J. Chem. Soc., Dalton

Trans. 1996, 2547. (f) Nombel, P.; Lugan, N.; Mathieu, R. J. Orga-

nomet. Chem. 1995, 503, C22. (g) Bruce, M. I.; Swincer, A. G.; Wallis,

R. C. J. Organomet. Chem. 1979, 171, C5.

(3) (a) Cadierno, V.; Gamasa, M. P.; Gimeno, J.; Iglesias, L.; Garcia-

Granda, S. Inorg. Chem. 1999, 38, 2874. (b) Gamasa, M. P.; Gimeno,

J.; Gonzalez-Bernardo, C.; Borge, J.; Garcia-Granda, S. Organometal-

lics 1997, 16, 2483. (c) Ru¨ba, E.; Slugovc, C.; Gemel, C.; Mereiter, K.;

Schmid, R.; Kirchner, K. Organometallics 1999, 18, 2275. (d) Bianchini,

C.; Peruzzini, M.; Romerosa, A.; Zanobini, F. Organometallics 1995,

14, 3152. (e) Barrett, A. G. M.; Carpenter, N. E. Organometallics 1987,

6, 2249. (f) Ouzzine, K.; Le Bozec, H.; Dixneuf, P. H. J. Organomet.

Chem. 1986, 317, C25. (g) Nombel, P.; Lugan, N.; Mathieu, R. J.

Organomet. Chem. 1995, 503, C22. (h) Le Bozec, H.; Ouzzine, K.;

Dixneuf, P. H. Organometallics 1991, 10, 2768.

* To whom correspondence should be addressed. E-mail: kkirch@

mail.zserv.tuwien.ac.at.

^†Institute of Applied Synthetic Chemistry.

^‡Institute of Chemical Technologies and Analytics.

(1) (a) Cadierno, V.; Gamasa, M. P.; Gimeno, J. Coord. Chem. Rev.

2004, 248, 1627. (b) Rigaut, S.; Touchard, D.; Dixneuf, P. H. Coord.

Chem. Rev. 2004, 248, 1585. (c) Guerchais, V. Eur. J. Inorg. Chem.

2002, 783. (d) Bruneau, C.; Dixneuf, P. H. Acc. Chem. Res. 1999, 32,

311. (e) Puerta, M. C.; Valerga, P. Coord. Chem. Rev. 1999, 193-195,

977. (f) Cadierno, V.; Diez, J.; Gamasa, M. P.; Gimeno, J.; Lastra, E.

Coord. Chem. Rev. 1999, 193-195, 147. (g) Bruce, M. I. Chem. Rev.

1998, 98, 2797. (h) Touchard, D.; Dixneuf, P. H. Coord. Chem. Rev.

1998, 178-180, 409. (i) Werner, H. J. Chem. Soc., Chem. Commun.

1997, 903. (j) Bruce, M. I. Chem. Rev. 1991, 91, 197.

(4) (a) Esteruelas, M. A.; Gomez, A. V.; Lopez, A. M.; Modrego, J.;

Onate, E. Organometallics 1998, 17, 5434. (b) Senn, D. R.; Wong, A.;

Patton, A. T.; Marsi, M.; Strouse, C. E.; Gladysz, J. A. J. Am. Chem.

Soc. 1988, 110, 6096.

(5) Ting, P. C.; Lin, Y. C.; Lee, G. H.; Cheng, M. C.; Wang, Y. J.

Am. Chem. Soc. 1996, 118, 6433.

Publication on Web 06/10/2005

3562 Organometallics, Vol. 24, No. 14, 2005

Pavlik et al.

Chart 1

Scheme 2

Structural views are depicted in Figures 1 and 2, with

selected bond distances and angles given in the captions.

In both complexes the steric requirements of the bulky

aminophosphine ligands lead to an an asymmetric

arrangement of the phenyl moieties. Both complexes are

stabilized in the solid state by intramolecular hydrogen

bonds between the two amino groups and/or between

the amino groups and the chloride ligand. In 1a two

markedly bent N-H‚‚‚Cl bonds with distinctly different

N‚‚‚C distances are observed (Figure 1), while in 2a‚

CHCl₃both an intramolecular N-H‚‚‚N bond and an

N-H‚‚‚Cl hydrogen bond are present (Figure 2). In

addition, 2a‚CHCl₃also contains an intramolecular

C-H‚‚‚Cl hydrogen interaction from the CHCl₃molecule

to the Ru complex: C(CHCl₃)‚‚‚Cl(Ru complex) ) 3.40

Å.

Scheme 1

In solution, even at temperatures of -90 °C in CD₂-

Cl₂as the solvent, only one ³¹P{¹H} signal is observed

for both complexes 1 and 2, indicating a rather weak

hydrogen bond and thus apparently fast exchange.

According to DFT/B3LYP calculations in the model

complex RuCp(PH₃)(PH₂NH₂)Cl intramolecular N-H‚

‚‚Cl hydrogen bonding provides a stabilization of merely

2.5 kcal/mol. It is, therefore, not surprising that this

weak interaction cannot be observed in solution by NMR

spectroscopy, even at very low temperatures.

tional ligands such 2-aminopyridine⁷and 2-acetami-

dopyridines.⁸

In the present paper we report on the synthesis of

RuCp and RuTp complexes containing phosphinoamine

ligands of the type PPh₂NHR with R ) Ph, n-Pr. We

describe the reactivity of these complexes toward ter-

minal acetylenes and propargylic alcohols, yielding

novel cyclic four-membered azaphosphacarbenes via an

intramolecular addition of the amine moiety of the

bifunctional phosphinoamine ligand to vinylidene and

allenylidene complexes according to Chart 1.

Substitution of the chloride ligand in 1a for the

-

weakly nucleophilic CF₃SO₃anion was investigated

Results and Discussion

Treatment of RuCp(PPh₃)₂Cl with an excess of PPh₂-

NHR (R ) Ph, n-Pr) at 120 °C for 12 h in toluene affords

RuCp(PPh₂NHR)₂Cl (1a,b) in 88 and 91% yields, re-

spectively (Scheme 1). The synthesis of 1a has been

already reported elsewhere.⁹The analogous RuTp com-

plexes RuTp(PPh₂NHR)₂Cl (2a,b) have been prepared

by reacting RuTp(COD)Cl with 2 equiv of PPh₂NHR at

120 °C for 3 h in toluene according to Scheme 2. All of

these complexes are air-stable and thermally robust

orange to yellow solids. They have been characterized

by a combination of elemental analysis and ¹H, ¹³C{¹H},

and ³¹P{¹H} NMR spectroscopy. In addition, 1a and 2a

have been characterized by X-ray crystallography.

Figure 1. Structural view of RuCp(PPh₂NHPh)₂Cl (1a)

showing 50% thermal ellipsoids. Selected bond lengths (Å)

and angles (deg): Ru-C(1-5)_av) 2.210(1), Ru-P(1) )

2.2798(3), Ru-P(2) ) 2.2947(3), Ru-Cl ) 2.4413(3), P(1)-

N(1) ) 1.681(1), P(2)-N(2) ) 1.693(1), N(1)-C(18) ) 1.398-

(2), N(2)-C(36) ) 1.403(2); P(1)-Ru-P(2) ) 97.52(1), P(1)-

Ru-Cl ) 90.78(1), P(2)-Ru-Cl ) 89.56(2), P(1)-N(1)-

C(18) ) 133.5(1), P(2)-N(2)-C(36) ) 129.5(1); N(1)‚‚‚C )

3.094(1), N(2)‚‚‚Cl ) 3.335(1).

(6) Trost, B. M.; Kulawiec, R. J. J. Am. Chem. Soc. 1992, 114, 5576.

(7) Standfest-Hauser, C. M.; Mereiter, K.; Schmid, R.; Kirchner, K.

Dalton 2003, 2329.

(8) Slugovc, C.; Mereiter, K.; Schmid, R.; Kirchner, K. Organome-

tallics 1998, 17, 827.

(9) Priya, S.; Balakrishna, M. S.; Mobin, S. M.; McDonald, R. J.

Organomet. Chem. 2003, 688, 227.

Four-Membered Azaphosphacarbenes

Organometallics, Vol. 24, No. 14, 2005 3563

Figure 3. Structural view of RuCp(PPh₂NHPh)₂(CF₃SO₃)

(3) showing 40% thermal ellipsoids. Selected bond lengths

(Å) and angles (deg): Ru-C(1-5)_av) 2.188(4), Ru-P(1) )

2.305(1), Ru-P(2) ) 2.315(1), Ru-O(1) ) 2.234(3), P(1)-

N(1) ) 1.680(3), P(2)-N(2) ) 1.680(3); P(1)-Ru-P(2) )

98.99(3), P(1)-Ru-O(1) ) 86.4(1), P(2)-Ru-O(1) ) 86.2-

(1), P(1)-N(1)-C(18) ) 131.4(3), P(2)-N(2)-C(36) ) 132.8-

(2); N(1)‚‚‚O(1) ) 2.935(4), N(2)‚‚‚O(3) ) 3.305(6).

Figure 2. Structural view of RuTp(PPh₂NHPh)₂Cl‚CHCl₃

(2a‚CHCl₃) showing 40% thermal ellipsoids (CHCl₃omitted

for clarity). Selected bond lengths (Å) and angles (deg):

Ru-N(2) ) 2.153(1), Ru-N(4) ) 2.142(1), Ru-N(6) )

2.083(1), Ru-P(1) ) 2.3105(5), Ru-P(2) ) 2.3125(4), Ru-

Cl ) 2.4436(4), P(1)-N(7) ) 1.695(1), P(2)-N(8) ) 1.688-

(1); P(1)-Ru-P(2) ) 96.29(1), P(1)-Ru-Cl ) 89.96(1),

P(2)-Ru-Cl ) 90.64(1), P(1)-N(7)-C(22) ) 134.5(1),

P(2)-N(8)-C(40) ) 134.2(1); N(7)‚‚‚Cl ) 3.096(1), N(8)‚‚‚

N(7) ) 3.087(2).

Scheme 3

with the intention of generating a reactive complex

bearing a weakly coordinating ligand occupying a latent

coordination site. In fact, chloride abstraction from 1a

with AgCF₃SO₃(1 equiv) affords, on workup, the

expected neutral complex RuCp(PPh₂NHPh)₂(η¹-OSO₂-

CF₃) (3), where CF₃SO₃^-is directly bound to the metal

center (Scheme 1). A structural view of 3 is depicted in

Figure 3 with selected bond distances and angles given

in the caption. The overall geometry of the complex,

which has the usual three-legged piano-stool structure,

is very similar to that of 1a with respect to Ru-C(Cp)

and Ru-P bond lengths and also with respect to the

spatial arrangement of the two aminophosphine ligands.

The CF₃SO₃^-anion is coordinated via the oxygen atom

in an η¹fashion with a Ru-O(1) distance of 2.234(2) Å

and a Ru-O(1)-S angle of 128.7(2)°. Moreover, as

outlined in Figure 3, there are two intramolecular N-H‚

‚‚O hydrogen bonds which contribute to the coherence

and asymmetry of the complex. Several other ruthenium

complexes with the η¹-OSO₂CF₃ligand are known and

have been structurally characterized.¹⁰

On the other hand, if chloride abstraction from 1a is

performed with AgSbF₆instead of AgCF₃SO₃, a different

reaction was observed, resulting in the formation of

[RuCp(κ²(P,P)-PPh₂NHC₆H₄PPh₂)(NH₂Ph)]⁺(4) in 90%

yield (Scheme 3). In the ¹H NMR spectrum of 4 the Cp

ring gives rise to a singlet at 4.61 ppm. The NH₂

hydrogen atoms of the aniline ligand exhibit two dou-

blets centered at 3.80 and 3.11 ppm with P-C coupling

constants of 11.2 and 10.7 Hz, respectively. In the ³¹P-

{¹H} NMR spectrum the κ²(P,P)-coordinated PPh₂-

NHC₆H₄PPh₂ligand displays an AX pattern with two

doublets centered at 103.1 and 48.5 ppm. The coupling

constant J_PPis 63.3 Hz. In addition to spectroscopic and

analytical characterization also the solid-state structure

of 4 was determined by single-crystal X-ray diffraction.

An ORTEP diagram is shown in Figure 4. Selected bond

distances and angles are reported in the caption. Ac-

cordingly, the complex adopts a three-legged piano-stool

(10) (a) Gemel, C.; Kalt, D.; Mereiter, K.; Sapunov, V. N.; Schmid,

R.; Kirchner, K. Organometallics 1997, 16, 427. (b) Sutter, J.-P.; James,

S. L.; Steenwinkel, P.; Karlen, T.; Grove, D. M.; Veldman, N.; Smeets,

W. J. J.; Spek, A. L.; van Koten, G. Organometallics 1996, 15, 941. (c)

Kraakman, M. J. A.; de Klerk-Engels, B.; de Lange, P. P. M.; Vrieze,

K.; Smeets, W. J. J.; Spek, A. L. Organometallics 1992, 11, 3774. (d)

Plosser, P. W.; Gallucci, J. C.; Wojcicki, A. Inorg. Chem. 1992, 31, 2376.

3564 Organometallics, Vol. 24, No. 14, 2005

Pavlik et al.

pounds have again been characterized by elemental

1

analysis and by H, ¹³C{¹H}, and ³¹P{¹H} NMR spec-

troscopy. Characteristic features comprise, in the ¹³C-

{¹H} NMR spectrum, a marked low-field doublet of

doublets resonance in the range of 275.8-282.3 ppm (dd,

J_CP) 31-33 Hz, J_CP) 12-14 Hz), assignable to the

carbene carbon atom of the four-membered azaphos-

phacarbene moiety. The ³¹P{¹H} NMR spectrum of

complexes 5 and 6 reveal two doublets centered at about

88-82 and 78-72 ppm with a small coupling constant

of 36 Hz. The NH proton of the PPh₂NHPh ligand gives

rise to a doublet at about 6.5-5.5 ppm (J_HP) 16-17

Hz), whereas the NH proton of the PPh₂NHPrⁿligand

could not be detected. Finally, the ¹H and ¹³C{¹H} NMR

resonances of the Cp ligand are in the expected ranges.

Metallacyclobutene complexes of the type A, where

X and/or Y are, e.g., C, N, O, S, or P moieties are

comparatively rare (Chart 2).¹³Four-membered aza-

phosphacarbene complexes where X ) PR₂and Y ) NR,

according to our knowledge, have not been described in

the literature. In the last couple of years, Cavell and

others reported the synthesis of a series of transition-

metal bis(iminophosphorano)carbene complexes which

are somewhat related to azaphosphacarbenes. In these

compounds the carbene moiety is a four-membered

chelate ligand coordinated in κ²(C,N) fashions of the

types B-D.¹⁴Structures of the “pincer type” B include

group 4 metals,¹⁵samarium,¹⁶and molybdenum.¹⁷The

bridged species C is observed in chromium,¹⁸alumi-

num,¹⁹and group 14 metals,²⁰while bis(iminophospho-

rano)carbene complexes acting as a κ²(C,N) bidentate

ligand (D) are found in platinum²¹and ruthenium

complexes.²²

Figure 4. Structural view of [RuCp(κ²(P,P)-PPh₂NHC₆H₄-

PPh₂)(NH₂Ph)]SbF₆‚solv (4‚solv) showing 40% thermal

ellipsoids (SbF₆^-and solvent omitted for clarity). Selected

bond lengths (Å) and angles (deg): Ru-C(1-5)_av) 2.214-

(5), Ru-P(1) ) 2.271(2), Ru-P(2) ) 2.285(2), Ru-N(2) )

2.238(5), P(1)-N(1) ) 1.692(5); P(1)-Ru-P(2) ) 86.92(5),

P(1)-Ru-N(2) ) 97.5(1), P(2)-Ru-N(2) ) 87.4(1), P(1)-

N(1)-C(18) ) 122.2(4), Ru-N(2)-C(36) ) 125.5(3).

conformation with the two phosphorus atoms of the

PPh₂NHC₆H₄PPh₂ligand and the nitrogen atom of the

aniline ligand as the legs. The Ru-P(1) and Ru-P(2)

bond distances are 2.271(2) and 2.285(2) Å, respectively,

with a P(1)-Ru-P(2) bite angle of 86.92(5)°. The Ru-

N(2) bond length is 2.238(5) Å with a Ru-N(2)-C(36)

angle of 125.5(3)°. For comparison, the Ru-N(aniline)

bond distances in the ruthenium aniline complexes

[RuTp(PMe₃)(NH₂Ph)]⁺and [RuTp(P(OMe)₃)(NH₂Ph)]⁺

are 2.211(3) and 2.182(2) Å, respectively.¹¹The respec-

tive Ru-N-C angles are 123.6(2) and 120.8(1)°.

Due to the absence of any observable intermediates

the mechanism of this reaction can only be speculated

upon. A possible mechanism is presented in Scheme 3.

Chloride abstraction may initially afford the highly

reactive coordinatively unsaturated 16e^-complex

[RuCp(PPh₂NHPh)₂]⁺(A),¹²which then undergoes ortho

metalation to yield the Ru(IV) hydride complex B.

Intramolecular hydride abstraction by the “built-in”

base PPh₂NHPh leads to the formation of C, which

subsequently undergoes reductive elimination, thereby

forming the new bidentate bisphosphine ligand PPh₂-

NHC₆H₄PPh₂and releasing free aniline. The latter

occupies the vacant coordination site, finally forming

complex 4. In the course of this reaction the P-N bond

of one PPh₂NHPh ligand is cleaved while a new P-C

bond is formed.

(13) For examples of four-membered metallacyclobutene complexes

containing at least one heteroatom, see: (a) Carlton, L.; Davidson, J.

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(b) Fischer, E. O.; Filippou, A. C.; Alt, H. G.; Thewalt, U. Angew. Chem.,

Int. Ed. Engl. 1985, 24, 203. (c) Bohle, D. S.; Clark, G. R.; Rickard, C.

E. F.; Roper, W. R.; Wright, L. J. J. Organomet. Chem. 1988, 358, 411.

(d) Licandro, E.; Maiorana, S.; Manzotti, R.; Papagni, A.; Perdiccia,

D.; Pryce, M.; Tiripiccio, A.; Lanfranchi, M. Chem. Commun. 1998, 383.

(e) Buil, M. L.; Esteruelas, M. A.; Garcia-Yebra, C.; Gutierrez-Puebla,

E.; Olivan, M. Organometallics 2000, 19, 2184. (f) Jamison, G. M.;

Saunders: R. S.; Wheeler, D. R.; Alam, T. M.; McClain, M. D.; Loy, D.

A.; Ziller, J. W. Organometallics 1996, 15, 3244. (g) Handwerker, B.

M.; Garnett, K. E.; Nagle, K. L.; Geoffroy, G. L.; Rheingold, A. L.

Organometallics 1990, 9, 1562. (h) Adams, R. D.; Chen, G. Organo-

metallics 1992, 11, 837. (i) Castarlenas, R.; Esteruelas, M. A.; Onate,

E. Organometallics 2001, 20, 2294.

(14) For a review, see: Cavell, R. G.; Kamalesh Babu, R. P.; Aparna,

K. J. Organomet. Chem. 2001, 617-618, 158.

(15) (a) Cavell, R. G.; Kamalesh Babu, R. P.; Kasani, A.; McDonald,

R. J. Am. Chem. Soc. 1999, 121, 5805. (b) Kamalesh Babu, R. P.;

McDonald, R.; Decker, S. A.; Klobukowski, M.; Cavell, R. G. Organo-

metallics 1999, 18, 4226. (c) Kamalesh Babu, R. P.; McDonald, R.;

Cavell, R. G. Chem. Commun. 2000, 481. (d) Kamalesh Babu, R. P.;

McDonald, R.; Cavell, R. G. Organometallics 2000, 19, 3462. (e)

Aparna, K.; Kamalesh Babu, R. P.; McDonald, R.; Cavell, R. G. Angew.

Chem., Int. Ed. 2001, 40, 4400.

Reaction of the [RuCp(PPh₂NHR)₂]⁺(R ) Ph,

n-Pr) Fragment with Terminal Alkynes. Treatment

of 1a,b with HCtCR′ (R′ ) Ph, p-C₆H₄Me, n-Bu) in the

presence of AgCF₃SO₃(1 equiv) at room temperature

for 2-12 h in CH₂Cl₂as the solvent results in the

formation of the novel azaphosphacarbene complexes

[RuCp(κ²(C,P)dC(CH₂R′)N(R)PPh₂)(κ¹(P)-PPh₂NHR)]⁺

(5a-c, 6a-c) in high yields (Scheme 4). These com-

(16) Aparna, K.; Ferguson, M.; Cavell, R. G. J. Am. Chem. Soc. 2000,

122, 726.

(17) Leung, W.-P.; So, C.-W.; Wang, J.-Z.; Mak, T. C. W. Chem.

Commun. 2003, 248.

(18) Kasani, A.; McDonald, R.; Cavell, R. G. Chem. Commun. 1999,

1993.

(19) (a) Aparna, K.; McDonald, R.; Ferguson, M.; Cavell, R. G.

Organometallics 1999, 18, 4241. (b) Aparna, K.; McDonald, R.; Cavell,

R. G. J. Am. Chem. Soc. 2000, 122, 9314. (c) Cavell, R. G.; Aparna, K.;

Kamalesh Babu, R. P.; Wang, Q. J. Mol. Catal. A 2002, 189, 137.

(20) Leung, W.-P.; Wang, Z.-X.; Li, H.-W.; Mak, T. C. W. Angew.

Chem., Int. Ed. 2001, 40, 2501.

(11) Conner, D.; Jayaprakash, K. N.; Gunnoe, T. B.; Boyle, P. D.

Inorg. Chem. 2002, 41, 3042.

(12) Coordinatively unsaturated RuCp complexes, in contrast to

RuCp* complexes, seem to be extremely rare. For a recent example,

see: Gemel, C.; Huffman, J. C.; Caulton, K. G.; Mauthner, K.; Kirchner,

K. J. Organomet. Chem. 2000, 593-594, 342.

(21) Jones, N. D.; Lin, G.; Gossage, R. A.; McDonald, R.; Cavell, R.

G. Organometallics 2003, 22, 2832.

(22) Cadierno, V.; Diez, J.; Garcia-Alvarez, J.; Gimeno, J.; Calhorda,

M. J.; Veiros, L. F. Organometallics 2004, 23, 2421.

Four-Membered Azaphosphacarbenes

Organometallics, Vol. 24, No. 14, 2005 3565

Scheme 4

Chart 2

AgCF₃SO₃) with 1 equiv of water resulted in the

formation of the aminocarbene complexes [RuCp(d

C(CH₂R)NHPh)(PPh₂NHPh)(κ¹(P)-PPh₂OH)]⁺(8a,b), fea-

turing a κ¹(P)-coordinated diphenylphosphinous acid

(Scheme 5). Only a few examples of mononuclear

complexes with a single PPh₂OH ligand have been

reported in the literature, including W(CO)₄(PPh₂OH)-

(PPh₂CH₂COR) (R ) Ph, p-C₆H₄Me),²³PtCl₂(PPh₂OH),²⁴

[RuCp(PPh₂OH)₂(PHPh₂)]⁺, and [RuCp(PPh₂OH)-

(PHPh₂)₂]⁺.²⁵In many cases, the PPh₂OH ligand is

found in conjunction with the corresponding diphe-

nylphosphinite ligand, [PPh₂O]^-, to form Ph₂P-O-H‚

‚‚O-PPh₂moieties with very strong and almost sym-

metric hydrogen bonds of O‚‚‚O distances as low as 2.40

Å.

Complexes 8a,b are obviously formed via nucleophilic

attack of water at the phosphorus atom of the four-

membered azaphosphacarbene accompanied by con-

comitant cleavage of the P-N bond. The ¹H NMR

spectrum of 8a displays an AB pattern for the CH₂Ph

moiety, showing two doublets centered at 3.96 and 3.62

ppm with a coupling constant of 14.9 Hz. Furthermore,

the OH proton of the κ¹(P)-coordinated PPh₂OH ligand

in 8a and 8b gives rise to a low-field resonance at 11.68

and 10.75 ppm, respectively.

In contrast to the reactions of 1a,b and simple

terminal alkynes, with 3-butyn-1-ol oxacyclopentylidene

complexes of the type [CpRu(PPh₂NHR)₂(dC₄H₆O)]⁺

(7a,b) rather than azaphosphacarbenes are readily

formed (Scheme 4).

The formation of both azaphosphacarbene and oxacy-

clopentylidene complexes likely proceeds via vinylidene

intermediates according to Scheme 4. Although such

intermediates could not be isolated in the case of the

present RuCp systems, they could be spectroscopically

detected. The tendency of vinylidene complexes to be

readily attacked by nitrogen or oxygen donors to give

Fischer carbene complexes is well-known.^2,3

Such a process is especially facile when the nucleo-

philic attack occurs in an intramolecular, chelate-

assisted fashion. In the case of 3-butyn-1-ol, nucleophilic

addition of the hydroxy function of the alkynol at the

R-carbon atom of the vinylidene intermediate is appar-

ently kinetically favored over nucleophilic attack of the

amine moiety, thus yielding exclusively oxacyclopen-

tylidene complexes 7a,b.

While complexes 5a-c and 6a-c are air stable in the

solid state and to some extent also in solution, com-

plexes 5a-c, in sharp contrast to 6a-c, turned out to

be quite sensitive toward even traces of water. Accord-

ingly, treatment of 5a or 5c (either isolated or prepared

in situ by reacting 1a with the respective acetylene and

Characteristic ¹³C{¹H} NMR spectroscopic features of

8a and 8b comprise a marked low-field resonance at

254.3 and 258.7 ppm, respectively, assignable to the

carbene carbon atom of the aminocarbene moiety. The

³¹P{¹H} NMR spectrum of 8 displays an AX pattern,

showing two doublets centered at about 140 and 80 ppm,

assignable to the PPh₂OH and PPh₂NHPh ligands,

respectively. Attempts to grow crystals of complex 8b

failed; instead, small amounts of crystals identified as

the cationic [RuCp(dC(CH₂Buⁿ)NHPPh₂)(κ²(P,P)-PPh₂-

(23) Al-Jibori, S.; Hall, M.; Hutton, A. T.; Shaw, B. L. J. Chem. Soc.,

Dalton Trans. 1984, 863.

(24) Berry, D. E.; Beveridge, K. A.; Bushnell, G. W.; Dixon, K. R.

Can. J. Chem. 1985, 63, 863.

(25) Torres-Lubian, R.; Rosales-Hoz, M. J.; Arif, A. M.; Ernst, R.

D.; Paz-Sandoval, M. A. J. Organomet. Chem. 1999, 585, 68.

3566 Organometallics, Vol. 24, No. 14, 2005

Pavlik et al.

Scheme 5

OPPh₂)]⁺(9) could be obtained. Complex 9 contains a

symmetric κ²(P,P)-coordinated PPh₂OPPh₂ligand, as is

readily apparent from ³¹P{¹H} NMR spectroscopy,

exhibiting a singlet at 137.7 ppm. A structural view of

9 is depicted in Figure 5. Selected bond distances and

angles are reported in the caption. This complex can be

described in terms of a three-legged piano-stool confor-

mation with the two P atoms of the PPh₂OPPh₂ligand

and the C atom of the aminocarbene moiety as the legs.

The Ru-C(36) bond distance of 2.037(3) Å is comparable

to that of other heteroatom-stabilized ruthenium car-

bene complexes. The bite angle of the chelating PPh₂-

OPPh₂ligand is 67.91(2)°, corresponding to a P-P

distance of 2.51 Å. Only a very few complexes with a

chelating PPh₂OPPh₂ligand have been characterized

by now, examples being Cr(CO)₄(PPh₂OPPh₂)²⁶and

RuCl₂(PPh₂OPPh₂)(PPh₃)(Ph₂PO₂CCHdCH₂).²⁷In other

instances the ligand is acting as a bridging ligand,

showing in these cases P-P distances about 0.5 Å larger

than in the chelating mode.²⁶

When a solution of 8a is passed through a column

charged with neutral Al₂O₃, the PPh₂OH ligand is

readily deprotonated and RuCp(dC(CH₂Ph)NHPh)-

(PPh₂NHPh)(κ¹(P)-PPh₂O) (10a) is obtained (Scheme 5).

The diphenylphosphinite ligand is coordinated via the

lone pair at P rather than via the oxygen lone pairs.

This type of complex could be obtained also by directly

reaction of 5 with water and subsequent treatment with

acidic Al₂O₃, as shown for example for 5b, affording 10b

upon workup. Complexes 10 exhibit spectroscopic fea-

tures very similar to those of 8, and it is sufficient to

point out the ³¹P{¹H} NMR resonances giving rise to

two doublets centered at about 111 and 79.1 ppm,

assignable to the [PPh₂O]^-ligand and the aminophos-

phine PPh₂NHPh, respectively (cf. κ¹(P)-coordinated

PPh₂OH in 8a,b exhibits a ³¹P{¹H} signal at 141.0 and

140.8 ppm, respectively). On the basis of the ³¹P{¹H}

NMR data the phosphorus atom in [PPh₂O]^-may be

considered as P(III) rather than as P(V), and thus the

ligand is better described by structure IIa rather than

IIb. The formation of complexes 10 is reversible. In fact,

addition of acid, e.g. CF₃COOH, leads to a clean back-

transformation to 8, as monitored by NMR spectroscopy.

To unequivocally establish the ligand arrangement

around the metal center, the structure of 10a has been

determined by X-ray crystallography. A structural view

of 10a is depicted in Figure 6. Important bond distances

and angles are given in the caption. The molecule

exhibits the typical three-legged piano-stool geometry

Figure 5. Structural view of [RuCp(dC(CH₂Buⁿ)NHPPh₂)-

(κ²(P,P)-PPh₂OPPh₂)]CF₃SO₃(9) showing 20% thermal

-

ellipsoids (CF₃SO₃omitted for clarity). Selected bond

lengths (Å) and angles (deg): Ru-C(1-5)_av) 2.234(2), Ru-

P(1) ) 2.2508(5), Ru-P(2) ) 2.2439(5), Ru-C(36) ) 2.037-

(2), P(1)-O ) 1.673(1), P(2)-O ) 1.675(1), C(36)-N )

1.313(2), C(36)-C(37) ) 1.516; P(1)-Ru-P(2) ) 67.91(2),

P(1)-Ru-C(36) ) 99.1(1), P(2)-Ru-C(36) ) 90.8(1), P(1)-

O-P(2) ) 97.2(1); N‚‚‚O(1) ) 2.821(5).

(26) (a) Wang, E. H.; Prasad, L.; Gabe, E. J.; Bradley, F. C. J.

Organomet. Chem. 1982, 236, 321. (b) Burrows, A. D.; Mahon, M. F.;

Palmer, M. T.; Varrone, M. Inorg. Chem. 2002, 41, 1695.

(27) Irvine, D. J.; Preston, S. A.; Cole-Hamilton, D. J.; Barnes, J. C.

J. Chem. Soc., Dalton Trans. 1991, 2413.

Four-Membered Azaphosphacarbenes

Organometallics, Vol. 24, No. 14, 2005 3567

Figure 7. Structural view of [CpRu(PPh₂NHPh)₂(dCdCd

CPh₂)]CF₃SO₃‚CH₂Cl₂(11‚CH₂Cl₂) showing 40% thermal

Figure 6. Structural view of [RuCp(dC(CH₂Ph)NHPh)-

(PPh₂NHPh)(κ¹(P)-OdPPh₂)] (10a) showing 20% thermal

ellipsoids. Selected bond lengths (Å) and angles (deg): Ru-

C(1-5)_av) 2.237(9), Ru-P(1) ) 2.228(5), Ru-P(2) ) 2.282-

(5), Ru-C(42) ) 1.984(12), P(1)-N ) 1.678(10), P(2)-O )

1.534(7), C(42)-N(2) ) 1.352(14), C(42)-C(43) ) 1.509-

(15); P(1)-Ru-P(2) ) 94.5(1), P(1)-Ru-C(42) ) 87.3(4),

P(2)-Ru-C(42) ) 90.0(4), P(1)-N(1)-C(18) ) 132.2(8);

N(1)‚‚‚O ) 2.843(13), N(2)‚‚‚O ) 2.662(13).

-

ellipsoids (CF₃SO₃and CH₂Cl₂omitted for clarity). Se-

lected bond lengths (Å) and angles (deg): Ru-C(1-5)_av

)

2.250(4), Ru-P(1) ) 2.294(2), Ru-P(2) ) 2.297(2), Ru-

C(42) ) 1.889(6), C(42)-C(43) ) 1.270(8), C(43)-C(44) )

1.356(8), P(1)-N(1) ) 1.680(5), P(2)-N(2) ) 1.662(5); P(1)-

Ru-P(2) ) 97.92(6), P(1)-Ru-C(42) ) 89.3(2), P(2)-Ru-

C(42) ) 88.6(2), Ru-C(42)-C(43) ) 175.5(5), C(42)-C(43)-

C(44) ) 172.9(7), P(1)-N(1)-C(18) ) 131.3(4), P(2)-N(2)-

C(36) ) 131.0(4); N(1)‚‚‚C(31) ) 3.464(7), N(2)‚‚‚O(1) )

3.455(8).

with Ru-C(Cp), Ru-P, and Ru-C_carbenebond lengths

in accordance with other RuCp complexes of this work.

Interestingly, the Ru-P bond to the phosphinoamine

is slightly shorter than to the diphenylphosphinite

(2.228 vs 2.282 Å), which is one argument supporting

formula IIa. Another argument is the strong basicity

of the phosphinite oxygen atom, which becomes appar-

ent by the two outstandingly short intramolecular N-H‚

‚‚O hydrogen bonds of N‚‚‚O ) 2.66 and 2.84 Å present

in 10a (cf. Figure 6). The shorter of these two hydrogen

bonds compares well with those between [HNEt₃]⁺

cations and anionic phosphinite complexes.²⁸

caption. The structure shows the typical pseudo-

octahedral three-legged piano-stool geometry, with a

nearly linear allenylidene group coordinated to the

ruthenium atom. The allenylidene chain shows typical

Ru-C_R, C_R-C_â, and C_â-C_γbond lengths of 1.889(6),

1.270(8), and 1.356(8) Å comparing well with those of

related allenylidene complexes.^3b,29

The ¹H and ¹³C{¹H} NMR spectra of 12 are consistent

with the presence of an azaphosphacarbene structure

containing a vinyl side chain. In the ¹³C{¹H} NMR

spectrum of 12 the carbene moiety is identified by a

downfield signal at 275.2 ppm (dd, J_CP) 31.1 Hz, J_CP

) 15.0 Hz). Other spectral changes accompanying the

transformation to the azaphosphacarbene include char-

acteristic resonances at 148.0 and 92.7 ppm assignable

to the vinyl carbon atoms CHdCPh₂and CHdCPh₂,

respectively. The vinyl proton gives rise to a singlet at

5.08 ppm.

Next we have studied the reaction of complexes 1a,b

with the propargylic alcohol HCtCCPh₂OH in the

presence of AgCF₃SO₃. The outcome of this reaction

depends strongly on the nature of the subtituent of

the amine moiety in PPh₂NHR. In the case of R ) Ph,

the allenylidene complex [CpRu(PPh₂NHPh)₂(dCdCd

CPh₂)]⁺(11) is obtained in high yield. On the other

hand, with R ) n-Pr the amine moiety is more basic as

well as sterically less demanding; the reaction does not

stop at the stage of the allenylidene complex, and

nucleophilic attack of the amine moiety at the C_Ratom

of the allenylidene ligand leads to the formation of the

azaphosphacarbene [RuCp(κ²(C,P)dC(CHdCPh₂)N(Prⁿ)-

PPh₂)(κ¹(P)-PPh₂NHPrⁿ)]⁺(12), as outlined in Scheme

6. Complexes 11 and 12 are both air-stable solids and

Reaction of the [RuTp(PPh₂NHR)₂]⁺(R ) Ph,

n-Pr) Fragment with Terminal Alkynes. When 2a,b

is treated with HCtCR′ (R′ ) Ph, p-C₆H₄Me, n-Bu) in

the presence of either AgSbF₆or AgCF₃SO₃(1 equiv)

at room temperature for 4-24 h in CH₂Cl₂, the aza-

phosphacarbene complexes [RuTp(κ²(C,P)dC(CH₂R′)N-

(R)PPh₂)(κ¹(P)-PPh₂NHR)]⁺(14a,b, 15a-c) are obtained

in high yields as air-stable dark yellow solids (Scheme

7). The only exception is when HCtCBuⁿis reacted with

2a, where the vinylidene complex [RuTp(PPh₂NHPh)₂-

(dCdCH(Buⁿ)]SbF₆(13) was isolated. Complex 13 did

not undergo rearrangement to the corresponding aza-

phosphacarbene even under reflux conditions for 24 h.

1

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

spectroscopy and elemental analysis. Characteristic

spectroscopic features of 11 are the three resonances

in the ¹³C{¹H} NMR spectrum at 291.9, 201.5, and 161.2

ppm for the C_R, C_â, and C_γallenyl carbon atoms. A view

of the molecular geometry of 11 is shown in Figure 7,

with selected bond distances and angles given in the

(29) (a) Bustelo, E.; Jimenez Tenorio, M.; Puerta, M. C.; Valerga,

P. Eur. J. Inorg. Chem. 2001, 2391. (b) Bustelo, E.; Jimenez Tenorio,

M.; Puerta, M. C.; Valerga, P. Organometallics 1999, 18, 4563. (c)

Cadierno, V.; Gamasa, M. P.; Gimeno, J.; Lastra, E.; Borge, J.; Garcia-

Granda, S. Organometallics 1994, 13, 745.

(28) (a) Zeiher, C.; Hiller, W.; Lorenz, I.-P. Chem. Ber. 1985, 118,

3127. (b) Irvine, D. J.; Cole-Hamilton, D. J.; Barnes, J. C.; Howie, R.

A. Acta Crystallogr., Sect. C: Cryst. Struct. Commun. 1994, 50, 1222.

3568 Organometallics, Vol. 24, No. 14, 2005

Pavlik et al.

Scheme 6

Scheme 7

are found for 15b: Ru-C(40) is 1.993(1) Å, and Ru-

P(1) and Ru-P(2) distances are 2.323(1) and 2.253(1)

Å, respectively.

Upon treatment of 2a,b with the propargylic alcohol

HCtCPh₂OH and AgCF₃SO₃in CH₂Cl₂for 8 h at room

temperature, the allenylidene complexes [RuTp(PPh₂-

NHR)₂(dCdCdCPh₂)]⁺(16a,b) are obtained in high

yields (Scheme 8). These complexes are readily identi-

fied by ¹³C{¹H} NMR spectroscopy, exhibiting triplets

at 312.9 and 316.9 ppm with P-C coupling constants

of 19.1 and 19.9 Hz, respectively, which are assigned to

the C_Rcarbon atom of the allenylidene unit. The C_âand

C_γcarbon atoms give rise to singlets at 199.6 and 206.1

and at 164.1 and 160.9, respectively. While allenylidene

16a is stable even at elevated temperatures, 16b slowly

rearranges at 50 °C to afford the vinyl azaphosphacar-

bene complex [RuTp(κ²(C,P)dC(CHdCPh₂)N(Prⁿ)PPh₂)-

Complexes 14 and 15 exhibit three distinct sets of

1

pyrazol-1-yl resonances in a 1:1:1 ratio in the H and

¹³C{¹H} NMR spectrum, due to three distinct pyrazol-

1-yl rings differing in their trans ligand atoms. In the

¹³C{¹H} NMR spectrum the most noticeable resonance

is again the low-field resonance of the carbene carbon

atom, observed as a doublet of doublets in the range

288.5-283.7 ppm with P-C coupling constants between

1

20-23 Hz and 10-11 Hz. Finally, the H and ¹³C{¹H}

NMR resonances of Tp and the phosphinoamine ligands

are in the expected ranges.

The identities of the chemical structures of 14a and

15b were unequivocally proven by X-ray crystallogra-

phy. The result is depicted in Figures 8 and 9, respec-

tively, with important bond distances and angles given

in the captions. The coordination geometry around

ruthenium is a distorted octahedron. The three Ru-

N(Tp) bond lengths show only minor variations and are

within the range of those for other RuTp complexes. In

14a the Ru-C(28) bond distance is 2.007(14) Å, which

is comparable to those in other aminocarbene com-

plexes. The Ru-P(1) and Ru-P(2) distances are 2.241-

(4) and 2.333(4) Å, respectively. Similar bond distances

Figure 8. Structural view of [RuTp(κ²(C,P)dC(CH₂Ph)N-

(Ph)PPh₂)(κ¹(P)-PPh₂NHPh)]SbF₆‚2C₆H₅F (14a‚2C₆H₅F)

showing 20% thermal ellipsoids (SbF₆^-and C₆H₅F omitted

for clarity). Selected bond lengths (Å) and angles (deg):

Ru-N(2) ) 2.174(7), Ru-N(4) ) 2.112(7), Ru-N(6) )

2.121(7), Ru-P(1) ) 2.241(4), Ru-P(2) ) 2.333(4), Ru-

C(28) ) 2.007(14), C(28)-N(7) ) 1.334(16), P(1)-N(7) )

1.782(12), P(2)-N(8) ) 1.675(11); P(1)-Ru-P(2) ) 94.7-

(2), P(1)-Ru-C(28) ) 68.7(4), P(2)-Ru-C(28) ) 98.2(4).

Four-Membered Azaphosphacarbenes

Organometallics, Vol. 24, No. 14, 2005 3569

Scheme 8

(κ¹(P)-PPh₂NHPrⁿ)]CF₃SO₃(17) in high isolated yield

(Scheme 8). The NMR spectroscopic features are similar

to those of 5, 6, 14, and 15. The characteristic resonance

of the carbene carbon atom is 274.8 ppm (dd, J_CP) 22.2

Hz, J_CP) 13.0 Hz). In the ¹H NMR spectrum the vinyl

CHdCPh₂hydrogen atom gives rise to a doublet at 5.07

ppm (J_HP) 7.3 Hz). The solid-state structure of 17 has

been confirmed by single-crystal X-ray diffraction (Fig-

ure 10). Selected bond distances and angles are reported

in the caption. The coordination geometry around

ruthenium is distorted octahedral. The Ru-N(Tp) bond

distances are all very similar. The bond lengths in the

Ru-azaphosphacarbene ring are comparable to those

of complexes 14a and 15b: e.g. Ru-P(2) ) 2.260 Å, Ru-

C(40) ) 2.012 Å, P(2)-N(8) ) 1.766 Å, and N(8)-C(40)

) 1.353 Å in 17. Unlike in 14a but as in 15b this ring

is not planar in 17, as the nitrogen N(8) deviates by 0.25

Å from the plane defined by Ru, P(2), and C(40).

NHR with R ) Ph, n-Pr have been synthesized. We have

demonstrated that both the [RuCp(PPh₂NHR)₂]⁺and

[RuTp(PPh₂NHR)₂]⁺fragments prepared in situ pro-

mote the formation of vinylidene, allenylidene, and

oxacyclopentyldiene complexes upon treatment with

terminal alkynes. The strong electrophilic character of

the R-carbon atom of the vinylidene and allenylidene

unit, respectively, is demonstrated by the fact that the

weakly nucleophilic nitrogen atom of the bifunctional

phosphinoamine reacts readily with the vinylidene and

allenylidene moieties in an intramolecular fashion to

give novel cyclic azaphosphacarbene complexes. Aza-

phosphacarbenes belong to a rare series of transition-

metal complexes in which the carbene moiety is part of

a four-membered chelate ligand coordinated in a κ²(C,P)

mode.

Experimental Section

General Information. Manipulations were performed

under an inert atmosphere of purified argon by using Schlenk

techniques and/or a glovebox. All chemicals were standard

Concluding Remarks

In the present study RuCp and RuTp complexes

featuring two phosphinoamine ligands of the type PPh₂-

Figure 9. Structural view of [RuTp(κ²(C,P)dC(CH₂-

C₆H₄Me)N(Prⁿ)PPh₂)(κ¹(P)-PPh₂NHPrⁿ)]CF₃SO₃‚CH₂Cl₂-

Figure 10. Structural view of [RuTp(κ²(C,P)dC(CHd

CPh₂)N(Prⁿ)PPh₂)(κ¹(P)-PPh₂NHPrⁿ)]CF₃SO₃(17) showing

-

(15b‚CH₂Cl₂) showing 30% thermal ellipsoids (CF₃SO₃

30% thermal ellipsoids (CF₃SO₃omitted for clarity).

and CH₂Cl₂omitted for clarity). Selected bond lengths (Å)

and angles (deg): Ru-N(2) ) 2.166(1), Ru-N(4) ) 2.144-

(1), Ru-N(6) ) 2.168(1), Ru-P(1) ) 2.323(1), Ru-P(2) )

2.253(1), Ru-C(40) ) 1.993(1), C(40)-N(8) ) 1.351(2),

P(2)-N(8) ) 1.754(1), P(1)-N(7) ) 1.670(1); P(1)-Ru-P(2)

) 99.18(1), P(1)-Ru-C(40) ) 98.67(3), P(2)-Ru-C(40) )

67.46(3), P(1)-N(7)-C(22) ) 124.7(1), P(2)-N(8)-C(40) )

98.6(1), P(2)-N(8)-C(37) ) 131.4(1).

Selected bond lengths (Å) and angles (deg): Ru-N(2) )

2.163(1), Ru-N(4) ) 2.129(1), Ru-N(6) ) 2.154(1), Ru-

P(1) ) 2.3354(3), Ru-P(2) ) 2.2595(3), Ru-C(40) ) 2.012-

(1), C(40)-N(8) ) 1.353(1), P(2)-N(8) ) 1.766(1), P(1)-

N(7) ) 1.667(1); P(1)-Ru-P(2) ) 99.49(1), P(1)-Ru-C(40)

) 100.68(3), P(2)-Ru-C(40) ) 67.32(3), P(1)-N(7)-C(22)

) 124.4(1), P(2)-N(8)-C(40) ) 98.4(1), P(2)-N(8)-C(37)

) 131.0(1).

3570 Organometallics, Vol. 24, No. 14, 2005

Pavlik et al.

reagent grade and used without further purification. The

solvents were purified according to standard procedures.³⁰The

deuterated solvents were purchased from Aldrich and dried

over 4 Å molecular sieves. RuCp(PPh₃)₂Cl and RuTp(COD)Cl

were prepared according to the literature.^{31,32 1}H, ¹³C{¹H}, and

³¹P{¹H} NMR spectra were recorded on Bruker Avance 250

and 300 spectrometers and were referenced to SiMe₄(¹H and

¹³C{¹H}) and H₃PO₄(85%) (³¹P{¹H}). ¹H and ¹³C{¹H} NMR

RuTp(PPh₂NHPrⁿ)₂Cl (2b). This complex has been pre-

pared analogously to 2a with RuTp(COD)Cl (150 mg, 0.20

mmol) and PPh₂NHPrⁿ(642.3 mg, 2.64 mmol) as starting

materials. Yield: 664 mg (90%). Anal. Calcd for C₃₉H₄₆-

BClN₈P₂Ru (mol wt 836.13): C, 56.02; H, 5.55; N, 13.40.

Found: C, 56.11; H, 5.67; N, 13.37. ¹H NMR (δ, CDCl₃, 20

°C): 7.86-7.02 (m, 23H, Ph, Tp), 6.75 (d, J ) 1.9 Hz, 2H, Tp),

5.75 (d, J ) 1.9 Hz, 1H, Tp), 5.62 (dd, J₁) J₂) 2.1 Hz, 2H,

Tp), 5.41 (dd, J₁) J₂) 2.2 Hz, 1H, Tp), 4.47-4.27 (m, 2H,

NHPrⁿ), 2.91-2.74 (m, 2H, Prⁿ), 2.70-2.47 (m, 2H, Prⁿ), 1.78-

1.54 (m, 4H, Prⁿ), 0.91 (t, J_HH) 7.4 Hz, 6H, Prⁿ). ¹³C{¹H} NMR

(δ, CDCl₃, 20 °C): 147.0 (Tp), 143.7 (Tp), 136.3 (t, ¹J_CP) 18.9

Hz, Ph¹), 135.4 (Tp), 134.9 (t, ¹J_CP) 13.1 Hz, Ph¹′), 134.2 (Tp),

1

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

and HSQC(¹H-¹³C) experiments.

RuCp(PPh₂NHPh)₂Cl (1a). A suspension of RuCp(PPh₃)₂-

Cl (1.5 g, 2.01 mmol) and PPh₂NHPh (4.6 g, 15.5 mmol) in

toluene (15 mL) was heated for 12 h at reflux. After removal

of the solvent, the remaining residue was dissolved in CH₂Cl₂

and precipitated with petroleum ether. The product was

collected on a glass frit, washed with petroleum ether, and

dried under vacuum. Yield: 1.4 g (88%). Anal. Calcd for C₄₁H₃₇-

ClN₂P₂Ru (mol wt 756.23): C, 65.12; H, 4.93; N, 3.70. Found:

2

132.8 (t, J_CP) 4.6 Hz, Ph^2,6), 132.5 (t, J_CP) 4.6 Hz, Ph^2′,6′),

3

128.7 (Ph⁴), 128.5 (Ph⁴′), 127.4 (t, J_CP) 4.2 Hz, Ph^3,5), 127.1

(t, ³J_CP) 4.2 Hz, Ph^3′,5′), 104.6 (Tp), 104.4 (Tp), 46.8 (t, J_CP

)

5.4 Hz, CH₂), 25.3 (t, J_CP) 3.1 Hz, CH₂), 11.9 (CH₃). ³¹P{¹H}

NMR (δ, CDCl_3,20 °C): 88.3.

1

RuCp(PPh₂NHPh)₂(η¹-OSO₂CF₃) (3). A solution of 1a

(100 mg, 0.13 mmol) in CH₂Cl₂(5 mL) was treated with AgCF₃-

SO₃(41 mg, 0.16 mmol) and stirred at room temperature for

2 h. The solution was then evaporated to dryness, and the

residue was redissolved in CH₂Cl₂. Insoluble materials were

removed by filtration. On addition of Et₂O a yellow precipitate

was formed, which was collected on a glass frit, washed with

Et₂O, and dried under vacuum. Yield: 82 mg (72%). Anal.

Calcd for C₄₂H₃₇F₃N₂O₃P₂RuS (mol wt 869.8): C, 57.99; H,

C, 65.09; H, 5.02; N, 4.67. H NMR (δ, CDCl₃, 20 °C): 7.56-

7.09 (m, 20H, Ph), 6.84 (t, J_HH) 8.0 Hz, 4H, NHPh), 6.59 (t,

J_HH) 7.4 Hz, 2H, NHPh), 6.33 (d, J_HH) 7.7 Hz, 4H, NHPh),

2

6.17 (pt, J_HP) 6.6 Hz, 2H, NHPh), 4.07 (5H, Cp). ¹³C{¹H}

NMR (δ, CDCl₃, 20 °C): 143.2 (t, J_CP) 6.7 Hz, NPh¹), 139.0

1

(t, J_CP) 25.0 Hz, Ph¹), 135.5 (t, J_CP) 25.1 Hz, Ph¹′), 131.6

2

(t, J_CP) 5.5 Hz, Ph^2,6), 131.2 (t, J_CP) 5.5 Hz, Ph^2,6′), 129.2

4

3

(d, J_CP) 3.7 Hz, Ph^4,4′), 128.3 (NPh^3,5), 127.8 (t, J_CP) 5.3

Hz, Ph^3,5), 127.7 (t, ³J_CP) 5.3 Hz, Ph^3,5′), 119.5 (NPh⁴), 117.9

(t, J_CP) 2.5 Hz, NPh^2,6), 81.5 (t, J_CP) 2.5 Hz, Cp). ³¹P{¹H}

NMR (δ, CDCl_3,20 °C): 71.9.

1

4.29; N, 3.22. Found: C, 57.80; H, 4.28; N, 3.17. H NMR (δ,

CDCl₃, 20 °C): 7.40-7.03 (m, 20H, Ph), 6.80 (t, J_HH) 7.8 Hz,

RuCp(PPh₂NHPrⁿ)₂Cl (1b). This complex has been pre-

pared analogously to 2a with RuCp(PPh₃)₂Cl (300 mg, 0.41

mmol) and PPh₂NHPrⁿ(603 mg, 2.5 mmol) as the starting

materials. Yield: 256 mg (91%). Anal. Calcd for C₃₅H₄₁ClN₂P₂-

Ru (mol wt 688.19): C, 61.09; H, 6.00; N, 4.07. Found: C,

60.94; H, 6.12; N, 4.00. ¹H NMR (δ, CDCl₃, 20 °C): 7.75-7.64

(m, 4H, Ph), 7.38-7.22 (m, 8H, Ph), 7.20 - 7.09 (m, 4H, Ph),

4.07-6.93 (m, 4H, Ph), 4.28-3.29 (m, 2H, NHPrⁿ), 4.14 (5H,

Cp), 2.52-2.36 (m, 2H, Prⁿ), 2.33-2.16 (m, 2H, Prⁿ), 1.52-

1.33 (m, 4H, Prⁿ), 0.81 (t, J_HH) 7.4 Hz, 6H, Prⁿ). ¹³C{¹H} NMR

(δ, CDCl₃, 20 °C): 140.2 (t, ¹J_CP) 21.0 Hz, Ph¹), 137.8 (t, ¹J_CP

4H, NHPh), 6.57 (t, J_HH) 7.2 Hz, 2H, NHPh), 6.28 (d, J_HH

)

2

7.9 Hz, 4H, NHPh), 5.49 (pt, J_HP) 8.0 Hz, 2H, NHPh), 4.20

(5H, Cp). ¹³C{¹H} NMR (δ, CDCl₃, 20 °C): 142.2 (t, J_CP) 6.2

Hz, NPh¹), 137.0 (t, ¹J_CP) 26.0 Hz, Ph¹), 134.3 (t, ¹J_CP) 24.6

2

Hz, Ph¹′), 131.3 (t, J_CP) 5.8 Hz, Ph^2,6), 131.0 (t, J_CP) 6.0

Hz, Ph^2,6′), 129.9 (Ph⁴), 129.7 (Ph⁴′), 128.4 (NPh^3,5), 128.3 (t,

³J_CP) 5.1 Hz, Ph^3,5), 128.3 (t, J_CP) 5.3 Hz, Ph^3,5′), 119.8

3

(NPh⁴), 117.9 (t, J_CP) 2.8 Hz, NPh^2,6), 84.0 (Cp). ³¹P{¹H} NMR

(δ, CDCl_3,20 °C): 77.3.

[RuCp(K²(P,P)-PPh₂NHC₆H₄PPh₂)(NH₂Ph)]SbF₆(4). A

solution of complex 1a (100 mg, 0.13 mmol) in CH₂Cl₂(5 mL)

was treated with AgSbF₆(54.5 mg, 0.16 mmol) and stirred at

room temperature for 2 h. The solution was evaporated to

dryness and the residue dissolved in CH₂Cl₂. Insoluble materi-

als were filtered off. On addition of Et₂O a yellow precipitate

was formed, which was collected on a glass frit, washed with

Et₂O, and dried under vacuum. Yield: 112 mg (90%). Anal.

Calcd for C₄₁H₃₇F₆N₂P₂RuSb (mol wt 956.5): C, 51.48; H, 3.90;

2

) 28.3 Hz, Ph¹′), 132.6 (t, J_CP) 5.3 Hz, Ph^2,6), 130.9 (t, J_CP

) 5.8 Hz, Ph^2,6′), 129.0 (Ph⁴), 128.3 (Ph⁴′), 127.6 (t, ³J_CP) 4.8

Hz, Ph^3,5), 127.4 (t, J_CP) 4.8 Hz, Ph^3,5′), 80.7 (t, J_CP) 2.5

3

2

3

Hz, Cp), 45.9 (t, J_CP) 5.8 Hz, CH₂), 24.6 (t, J_CP) 3.4 Hz,

CH₂), 11.7 (CH₃). ³¹P{¹H} NMR (δ, CDCl₃, 20 °C): 84.8.

RuTp(PPh₂NHPh)₂Cl (2a). A suspension of RuTp(COD)-

Cl (100 mg, 0.22 mmol) and PPh₂NHPh (133.3 mg, 0.480

mmol) in toluene (5 mL) was heated for 3 h at reflux. After

removal of the solvent the remaining residue was dissolved

in CH₂Cl₂(2 mL) and the product was precipitated by addition

of Et₂O and petroleum ether. The yellow powder was collected

on a glass frit, washed with petroleum ether, and dried under

vacuum. Yield: 171 mg (86%). Anal. Calcd for C₄₅H₄₂BClN₈P₂-

Ru (mol wt 904.16): C, 59.78; H, 4.68; N, 12.39. Found: C,

1

N, 2.93. Found: C, 51.39; H, 3.99; N, 2.97. H NMR (δ, CD₂-

2

Cl₂, 20 °C): 7.93-6.29 (m, 29H, Ph), 5.64 (d, J_HP) 6.6 Hz,

1H, NH), 4.61 (5H, Cp), 3.80 (d, J_HP) 11.2 Hz, 1H, NH₂Ph),

3.11 (d, J_HP) 10.7 Hz, 1H, NH₂Ph). ¹³C{¹H} NMR (δ, CD₂Cl₂,

20 °C): 148.9 (NHPh¹), 146.0 (NH₂Ph¹), 135.7-119.4 (Ph), 82.1

(Cp). ³¹P{¹H} NMR (δ, CD₂Cl_2,20 °C): 103.1 (d, J_PP) 63.3

Hz), 48.5 (d, J_PP) 63.3 Hz).

[RuCp(K (C,P)dC(CH₂Ph)N(Ph)PPh₂)(K (P)-PPh₂NHPh)]-

1

59.89; H, 4.56; N, 12.44. H NMR (δ, C₆D₆, 20 °C): 8.32 (pt,

2

²J_HP) 7.3 Hz, 2H, NHPh), 7.75-6.71 (36H, Ph, NHPh, Tp),

5.71 (d, J ) 1.6 Hz, 1H, Tp), 5.66 (dd, J₁) J₂) 2.2 Hz, 1H,

Tp), 5.60 (dd, J₁) J₂) 1.9 Hz, 1H, Tp). ¹³C{¹H} NMR (δ,

CDCl₃, 20 °C): 147.7 (Tp), 143.9 (Tp), 142.6 (t, J_CP) 5.9 Hz,

CF₃SO₃(5a). A solution of 1a (100 mg, 0.13 mmol) in CH₂Cl₂

(5 mL) and phenylacetylene (42.8 µL, 0.39 mmol) was treated

with AgCF₃SO₃(41 mg, 0.16 mmol) and stirred at room

temperature for 12 h. The solution was then evaporated to

dryness and the residue redissolved in CH₂Cl₂. Insoluble

materials were removed by filtration. On addition of Et₂O and

petroleum ether a dark yellow precipitate was formed, which

was washed with Et₂O and petroleum ether and dried under

vacuum. Yield: 76 mg (78%). Anal. Calcd for C₅₀H₄₃F₃N₂O₃P₂-

RuS (mol wt 972.0): C, 61.74; H, 4.46; N, 2.86. Found: C,

61.69; H, 4.50; N, 2.87. ¹H NMR (δ, CD₂Cl₂, 20 °C): 7.85-

6.62 (m, 31H, Ph), 6.28 (d, J_HH) 7.7 Hz, 2H, NHPh), 6.11 (d,

J_HH) 7.7 Hz, 2H, NHPh), 5.53 (d, ²J_HP) 16.8 Hz, 1H, NHPh),

4.49 (5H, Cp), 4.14 (dd, J_1,HH) 14.3 Hz, J_2,HP) 4.0 Hz, 1H,

CH₂Ph), 3.82 (dd, J_1,HH) 14.3 Hz, J_2,HP) 1.2 Hz, 1H, CH₂-

Ph).¹³C{¹H} NMR (δ, CD₂Cl₂, 20 °C): 276.8 (dd, J_1,CP) 32.2

1

NPh¹), 136.0 (Tp), 137.3 (t, J_CP) 21.1 Hz, Ph¹), 134.3 (Tp),

2

132.9 (t, J_CP) 5.0 Hz, Ph^2,6), 132.2 (t, J_CP) 5.0 Hz, Ph^2,6′),

131.2 (t, ¹J_CP) 23.2 Hz, Ph¹′), 129.1 (Ph⁴), 128.8 (Ph⁴′), 128.6

(NPh^3,5), 127.6 (t, ³J_CP) 4.6 Hz, Ph^3,5), 127.4 (t, ³J_CP) 5.3 Hz,

Ph^3,5′), 119.9 (NPh⁴), 118.5 (NPh^2,6), 104.8 (Tp), 104.5 (Tp). ³¹P-

{¹H} NMR (δ, C₆D₆, 20 °C): 76.8.

(30) Perrin, D. D.; Armarego, W. L. F. Purification of Laboratory

Chemicals, 3rd ed.; Pergamon: New York, 1988.

(31) Bruce, M. I.; Hameister, C.; Swincer, A. G.; Wallis, R. C. Inorg.

Synthesis 1990, 28, 270.

(32) Gemel, C.; Trimmel, G.; Slugovc, C.; Kremel, S.; Mereiter, K.;

Schmid, R.; Kirchner, K. Organometallics 1996, 15, 3998.

Four-Membered Azaphosphacarbenes

Organometallics, Vol. 24, No. 14, 2005 3571

Hz, J_2,CP) 13.8 Hz, dC), 141.8-118.7 (Ph), 86 2 (Cp), 53.3 (d,

J_CP) 11.5 Hz, CH₂). ³¹P NMR (δ, CD₂Cl_2,20 °C): 83.7 (d, J_PP

) 36.0 Hz), 77.2 (d, J_PP) 36.0 Hz).

[RuCp(K²(C,P)dC(CH₂Buⁿ)N(Prⁿ)PPh₂)(K¹(P)-

PPh₂NHPrⁿ)]CF₃SO₃(6c). This complex has been prepared

analogously to 5a using 1b (100 mg, 0.15 mmol), 1-hexyne

(50.0 µL, 0.44 mmol), and AgCF₃SO₃(41.1 mg, 0.16 mmol) as

starting materials. Yield: 111 mg (84%). Anal. Calcd for

C₄₂H₅₁F₃N₂O₃P₂RuS (mol wt 883.95): C, 57.07; H, 5.82; N,

[RuCp(K²(C,P)dC(CH₂C₆H₄CH₃)N(Ph)PPh₂)(K¹(P)-

PPh₂NHPh)]CF₃SO₃(5b). This complex has been prepared

analogously to 5a with 1a (150 mg, 0.20 mmol), p-tolylacety-

lene (75.4 µL, 0.6 mmol), and AgCF₃SO₃(61 mg, 0.24 mmol)

as starting materials. Yield: 119 mg (60%). Anal. Calcd for

C₅₁H₄₅F₃N₈O₃P₂RuS (mol wt 986.0): C, 62.13; H, 4.60; N, 2.84.

Found: C, 62.24; H, 4.71; N, 2.57. ¹H NMR (δ, CD₂Cl₂, 20 °C):

1

3.17. Found: C, 57.12; H, 5.69; N, 3.22. H NMR (δ, CD₂Cl₂,

20 °C): 7.98-6.91 (m, 20H, Ph), 4.72 (5H, Cp), 3.69-3.40 (m,

1H), 3.37-3.13 (m, 1H), 3.09-2.86 (m, 1H), 2.79-2.60 (m, 1H),

2.59-2.35 (m, 2H), 2.33-2.10 (m, 2H), 1.83-1.18 (m, 8H), 0.93

(t, J_HH) 7.0 Hz, 3H), 0.80 (t, J_HH) 7.3 Hz, 3H), 0.56 (t, J_HH

) 7.4 Hz, 3H). The NH proton could not be detected. ¹³C{¹H}

NMR (δ, CD₂Cl₂, 20 °C): 280.5 (dd, J_CP) 32.2 Hz, J_CP) 14.6

Hz, dC), 138.5-118.1 (Ph), 84.9 (Cp), 53.7 (CH₂), 46.4 (d, J_CP

) 11.5 Hz, CH₂), 45.7 (d, J_CP) 10.5 Hz, CH₂), 31.8 (CH₂), 27.8

(CH₂), 24.2 (d, J_CP) 6.9 Hz, CH₂), 22.8 (CH₂), 22.3 (CH₂), 13.8

(CH₃), 10.9 (CH₃). ³¹P{¹H} NMR (δ, CD₂Cl₂, 20 °C): 88.4 (d,

J_PP) 37.2 Hz), 72.2 (d, J_PP) 37.2 Hz).

2

7.98-6.57 (m, 30H, Ph), 6.42 (d, J_HP) 13.1 Hz, 1H, NHPh),

6.21 (d, J_HH) 7.8 Hz, 2H, NHPh), 6.15 (d, J_HH) 7.8 Hz, 2H,

NHPh), 4.46 (5H, Cp), 4.08 (dd, J_1,HH) 14.3 Hz, J_2,HP) 3.8

Hz, 1H, CH₂C₆H₄CH₃), 3.68 (d, J_HH) 14.3 Hz, 1H, CH₂C₆H₄-

CH₃), 2.41 (3H, CH₃).¹³C{¹H} NMR (δ, CD₂Cl₂, 20 °C): 277.0

(dd, J_1,CP) 32.2 Hz, J_2,CP) 13.8 Hz, dC), 141.5-118.7 (Ph),

86 2 (Cp), 52.8 (d, J_CP) 10.7 Hz, CH₂), 20.9 (CH₃). ³¹P{¹H}

NMR (δ, CD₂Cl_2,20 °C): 83.6 (d, J_PP) 35.6 Hz), 77.9 (d, J_PP

) 35.6 Hz).

[CpRu(PPh₂NHPh)₂(dC₄H₆O)]CF₃SO₃(7a). A solution of

1a (100 mg, 0.13 mmol) in CH₂Cl₂(5 mL) and 3-butyn-1-ol

(20 µL, 0.45 mmol) was treated with AgCF₃SO₃(37.4 mg, 0.15

mmol) and stirred at room temperature for 12 h. The solution

was then evaporated to dryness, and the residue was redis-

solved in CH₂Cl₂. Insoluble materials were removed by filtra-

tion. On addition of Et₂O and petroleum ether a light brown

precipitate was formed, which was washed with Et₂O and

petroleum ether and dried under vacuum. Yield: 85 mg (70%).

Anal. Calcd for C₄₆H₄₃F₃N₂O₄P₂RuS (mol wt 939.93): C, 58.78;

[RuCp(K²(C,P)dC(CH₂Buⁿ)N(Ph)PPh₂)(K¹(P)-

PPh₂NHPh)]CF₃SO₃(5c). This complex has been prepared

analogously to 5a using 1a (150 mg, 0.20 mmol), 1-hexyne

(68.9 µL, 0.6 mmol), and AgCF₃SO₃(61 mg, 0.24 mmol) as

starting materials. Yield: 102 mg (54%). Anal. Calcd for

C₄₈H₄₇F₃N₈O₃P₂RuS (mol wt 952.0): C, 60.50; H, 4.98; N, 2.94.

Found: C, 60.38; H, 4.88; N, 2.85. ¹H NMR (δ, CD₂Cl₂, 20 °C):

7.98-6.65 (m, 26H, Ph), 6.23 (d, J_HH) 8.0 Hz, 2H, NHPh),

2

6.13 (d, J_HH) 7.8 Hz, 2H, NHPh), 5.46 (d, J_HP) 16.7 Hz,

1

H, 4.61; N, 2.98. Found: C, 58.09; H, 4.73; N, 2.99. H NMR

NHPh), 4.84 (5H, Cp), 2.88-2.53 (m, 2H), 1.94-1.62 (m, 1H),

1.60-1.34 (m, 1H), 1.33-1.06 (m, 5H), 0.95-0.74 (m, 3H).¹³C-

{¹H} NMR (δ, CD₂Cl₂, 20 °C): 282.3 (dd, J_1,CP) 33.0 Hz, J_2,CP

(δ, CD₂Cl₂, 20 °C): 7.59-7.27 (m, 20H, Ph), 6.97 (t, J_HH) 8.0

Hz, 4H, NHPh), 6.79 (t, J_HH) 7.4 Hz, 2H, NHPh), 6.45 (d,

J_HH) 7.7 Hz, 4H, NHPh), 6.42 (pt, ²J_HP) 7.6 Hz, 2H, NHPh),

) 13.8 Hz, dC), 141.8-116.2 (Ph), 86.2 (Cp), 48.8 (d, J_CP

)

4.85 (5H, Cp), 4.49 (t, J_HH) 7.4 Hz, 2H, CH₂), 3.27 (t, J_HH

)

10.7 Hz, CH₂), 33.1 (CH₂), 21.8 (CH₂), 18.5 (CH₂), 13.8 (CH₃).

³¹P{¹H} NMR (δ, CD₂Cl₂, 20 °C): 81.9 (d, J_PP) 37.2 Hz), 77.6

(d, J_PP) 37.2 Hz).

7.7 Hz, 2H, CH₂), 1.84 (q, J_HH) 7.5 Hz, 2H, CH₂). ¹³C{¹H}

NMR (δ, CD₂Cl₂, 20 °C): 298.8 (t, J_CP) 13.3 Hz, dC), 141.5

1

(t, J_CP) 5.7 Hz, NPh¹), 136.2 (t, J_CP) 27.5 Hz, Ph¹), 135.7

n

1

2

[RuCp(K (C,P)dC(CH₂Ph)N(Pr )PPh₂)(K (P)-

PPh₂NHPrⁿ)]CF₃SO₃(6a). This complex has been prepared

analogously to 5a using 1b (100 mg, 0.15 mmol), phenylacety-

lene (32 µL, 0.29 mmol), and AgCF₃SO₃(41.1 mg, 0.16 mmol)

as starting materials. Yield: 105 mg (77%). Anal. Calcd for

C₄₄H₄₇F₃N₂P₂O₃RuS (mol wt 903.94): C, 58.46; H, 5.24; N,

(t, ¹J_CP) 29.1 Hz, Ph^1′), 131.2-128.4 (Ph), 121.2 (NPh⁴), 118.5

(t, J_CP) 2.8 Hz, NPh^2,6), 92.2 (t, J_CP) 1.8 Hz, Cp), 82.2 (CH₂),

59.5 (CH₂), 22.4 (CH₂). ³¹P{¹H} NMR (δ, CD₂Cl₂, 20 °C): 80.3.

[CpRu(PPh₂NHPrⁿ)₂(dC₄H₆O)]CF₃SO₃(7b). This com-

plex has been prepared analogously to 7a using 1b (100 mg,

0.15 mmol), 3-butyn-1-ol (109.7 µL, 1.45 mmol), and AgCF₃-

SO₃(41.1 mg, 0.16 mmol) as starting materials. Yield: 88 mg

(68%). Anal. Calcd for C₄₀H₄₇F₃N₂O₄P₂RuS (mol wt 871.89):

C, 55.10; H, 5.43; N, 3.21. Found: C, 55.06; H, 5.33; N, 3.12.

¹H NMR (δ, CD₂Cl₂, 20 °C): 7.98-7.23 (m, 20H, Ph), 4.83 (5H,

Cp), 4.51 (t, J_HH) 7.4 Hz, 2H), 4.27-4.09 (m, 2H, NHPrⁿ),

3.75 (t, J_HH) 6.0 Hz, 2H), 2.85 (t, J_HH) 7.7 Hz, 2H), 2.62-

2.33 (m, 5H), 1.74-1.58 (m, 1H), 1.58-1.39 (m, 2H), 0.87 (t,

J_HH) 7.7 Hz, 6H). ¹³C{¹H} NMR (δ, CD₂Cl₂, 20 °C): 297.8 (t,

1

3.10. Found: C, 58.39; H, 5.32; N, 3.17. H NMR (δ, CD₂Cl₂,

20 °C): 7.88-6.82 (m, 25H, Ph), 4.27 (5H, Cp), 3.48-3.24 (m,

1H, CH₂Ph), 3.48-3.24 (m, 1H, CH₂Ph), 2.71-2.46 (m, 1H,

Prⁿ), 2.43-2.2 (m, 1H, Prⁿ), 1.95-1.63 (m, 1H, Prⁿ), 1.59-1.32

(m, 1H, Prⁿ), 1.31-0.93 (m, 4H, Prⁿ), 0.81 (t, J_HH) 6.7 Hz,

3H, Prⁿ), 0.62 (t, J_HH) 7.3 Hz, 3H, Prⁿ). The NH proton could

not be detected. ¹³C{¹H} NMR (δ, CD₂Cl₂, 20 °C): 276.8 (dd,

J_CP) 32.2 Hz, J_CP) 14.6 Hz, dC), 135.7-127.8 (Ph), 85.0

(Cp), 54.1 (CH₂), 51.5 (CH₂), 46,0 (CH₂), 24.8 (CH₂), 23.1 (CH₂),

11.0 (CH₃), 10.8 (CH₃). ³¹P{¹H} NMR (δ, CD₂Cl₂, 20 °C): 88.7

(d, J_PP) 37.2 Hz), 74.5 (d, J_PP) 37.2 Hz).

1

J_CP) 14.2 Hz, dC), 137.8 (t, J_CP) 28.0 Hz, Ph¹), 136.8 (t,

¹J_CP) 29.5 Hz, Ph^1′), 133.9-128.3 (Ph), 91.9 (Cp), 81.6 (CH₂),

58.9 (CH₂), 45.6 (t, J_CP) 5.0 Hz, CH₂), 24.6 (t, J_CP) 3.5 Hz,

CH₂), 22.2 (CH₂), 11.3 (CH₃). ³¹P{¹H} NMR (δ, CD₂Cl₂, 20 °C):

87.3.

[RuCp(K²(C,P)dC(CH₂C₆H₄CH₃)N(Prⁿ)PPh₂)(K¹(P)-

PPh₂NHPrⁿ)]CF₃SO₃(6b). This complex has been prepared

analogously to 5a with 1b (100 mg, 0.15 mmol), p-tolylacety-

lene (36.8 µL, 0.29 mmol), and AgCF₃SO₃(41.1 mg, 0.16 mmol)

as starting materials. Yield: 103 mg (75%). Anal. Calcd for

C₄₅H₄₉F₃N₂O₂P₂RuS (mol wt 917.97): C, 58.88; H, 5.39; N,

[RuCp(dC(CH₂Ph)NHPh)(PPh₂NHPh)(K¹(P)-PPh₂OH)]-

CF₃SO₃(8a). A solution of 1 (150 mg, 0.20 mmol) in CH₂Cl₂

(5 mL) and phenylacetylene (65 µL, 0.6 mmol) was treated with

AgCF₃SO₃(56 mg, 0.22 mmol). H₂O (8 µL, 0.4 mmol,) was

added, and the reaction mixture was stirred at room temper-

ature for 12 h. The solution was evaporated to dryness and

the residue dissolved in CH₂Cl₂. Insoluble materials were

removed by filtration. Upon addition of Et₂O and petroleum

ether an orange precipitate was formed, which was washed

with Et₂O and petroleum ether and dried under vacuum.

Yield: 115 mg (58%). Anal. Calcd for C₅₀H₄₅F₃N₂O₄P₂RuS (mol

wt 990.0): C, 60.66; H, 4.58; N, 2.83. Found: C, 60.78; H, 4.50;

N, 2.77. ¹H NMR (δ, CD₂Cl₂, 20 °C): 11.68 (1H, PPh₂OH),

1

3.05. Found: C, 58.89; H, 5.44; N, 3.08. H NMR (δ, CD₂Cl₂,

20 °C): 7.97-6.71 (m, 25H, Ph), 4.26 (5H, Cp), 3.84-3.55 (m,

1H, CH₂C₆H₄Me), 3.51-3.27 (m, 1H, CH₂C₆H₄Me), 2.89-2.69

(m, 1H, Prⁿ), 2.67-2.47 (m, 1H, Prⁿ), 2.46-2.22 (m, 1H, Prⁿ),

2.38 (3H, CH₃), 1.87-1.65 (1H, Prⁿ), 1.58-1.05 (m, 4H, Prⁿ),

0.81 (t, J_HH) 7.4 Hz, 3H, Prⁿ), 0.60 (t, J_HH) 7.3 Hz, 3H, Prⁿ).

The NH proton could not be detected. ¹³C{¹H} NMR (δ, CD₂-

Cl₂, 20 °C): 275.8 (dd, J_CP) 31.4 Hz, J_CP) 14.6 Hz, dC),

138.1-118.1 (Ph), 84.9 (Cp), 54.0 (d, J_CP) 3.2 Hz, CH₂), 51.0

(d, J_CP) 12.3 Hz, CH₂), 45.8 (d, J_CP) 10.0 Hz, CH₂), 24.3 (d,

J_CP) 6.9 Hz, CH₂), 23.2 (CH₂), 20.8 (CH₃), 11.0 (CH₃), 10.8

(CH₃). ³¹P{¹H} NMR (δ, CD₂Cl₂, 20 °C): 88.8 (d, J_PP) 37.2

Hz), 74.4 (d, J_PP) 37.2 Hz).

2

7.96-6.84 (m, 29H, Ph), 6.82-6.53 (m, 6H, Ph), 6.46 (d, J_HP

) 7.2 Hz, 1H, NHPh), 6.23 (d, ²J_HP) 7.5 Hz, 1H, NHPh), 4.46

(5H, Cp), 3.96 (d, J_HH) 14.7 Hz, 1H, CH₂Ph), 3.62 (d, J_HH

)

3572 Organometallics, Vol. 24, No. 14, 2005

Pavlik et al.

14.9 Hz, 1H, CH₂Ph). ¹³C{¹H} NMR (δ, CD₂Cl₂, 20 °C): 254.3

(t, J_CP) 15.7 Hz, dC), 142.9-118.6 (Ph), 88.8 (Cp), 54.6 (CH₂).

³¹P{¹H} NMR (δ, CD₂Cl₂, 20 °C): 141.0 (d, J_PP) 47.1 Hz), 80.5

(d, J_PP) 47.1 Hz).

C, 64.58; H, 4.47; N, 2.64. Found: C, 64.63; H, 4.50; N, 2.72.

¹H NMR (δ, CD₂Cl₂, 20 °C): 7.97-6.96 (m, 30H, Ph), 6.84 (t,

J_HH) 7.9 Hz, 4H, NHPh), 6.71 (t, J_HH) 7.3 Hz, 2H, NHPh),

6.38 (dd, J_1,HP) 19.0 Hz, J_2,HP) 7.8 Hz, 2H, NHPh), 6.00 (d,

J_HH) 7.5 Hz, 4H, NHPh), 5.1 (5H, Cp). ¹³C{¹H} NMR (δ, CD₂-

Cl₂, 20 °C): 291.9 (dC), 201.5 (dCdCdCPh₂), 161.2 (dCdCd

CPh₂), 143.6-128.2 (Ph), 120.8 (NPh⁴), 118.1 (NPh^2,6), 93.0

(Cp). ³¹P{¹H} NMR (δ, CD₂Cl₂, 20 °C): 74.1.

[RuCp(dC(CH₂Buⁿ)NHPh)(PPh₂NHPh)(K¹-(P)-PPh₂OH)]-

CF₃SO₃(8b). This complex has been prepared analogously to

8a using 1 (150 mg, 0.20 mmol), 1-hexyne (68.9 µL, 0.6 mmol),

AgCF₃SO₃(61 mg, 0.24 mmol), and H₂O (8 µL, 0.4 mmol,) as

starting materials. Yield: 108 mg (56%). Anal. Calcd for

C₄₈H₄₉F₃N₂O₄P₂RuS (mol wt 970.0): C, 59.44; H, 5.09; N, 2.89.

Found: C, 59.39; H, 5.13; N, 2.67. ¹H NMR (δ, CD₂Cl₂, 20 °C):

10.75 (1H, PPh₂OH), 7.99-6.30 (m, 32H, Ph, NHPh), 4.71 (5H,

Cp), 2.70-2.41 (m, 2H, CH₂), 1.15-0.57 (m, 9H, Buⁿ). ¹³C{¹H}

NMR (δ, CD₂Cl₂, 20 °C): 258.7 (t, J_CP) 15.3 Hz, dC), 142.6

(d, ¹J_PC) 51.3 Hz, Ph¹), 142.2 (d, J_CP) 12.2 Hz, NPh¹), 140.4

n

1

2

[RuCp(K (C,P)dC(CHdCPh₂)N(Pr )PPh₂)(K (P)-

PPh₂NHPrⁿ)]CF₃SO₃(12). A solution of 1b (100 mg, 0.15

mmol) in CH₂Cl₂(5 mL) and 1,1-diphenylpropyn-1-ol (91 mg,

0.44 mmol) was treated with AgCF₃SO₃(41.1 mg, 0.16 mmol)

and stirred at room temperature for 1 h. The solution was then

evaporated to dryness and the residue redissolved in CH₂Cl₂.

Insoluble materials were removed by filtration. On addition

of Et₂O and petroleum ether a brown precipitate was formed,

which was washed with Et₂O and petroleum ether and dried

under vacuum. Yield: 93 mg (63%). Anal. Calcd for C₅₁H₅₁F₃N₂-

P₂O₃RuS (mol wt 992.05): C, 61.75; H, 5.18; N, 2.82. Found:

1

(d, J_PC) 47.5 Hz, Ph¹), 139.3 (NPh¹), 138.1 (d, J_PC) 52.9

Hz, Ph¹), 135.9 (d, ¹J_PC) 55.2 Hz, Ph¹), 132.7-118.5 (Ph), 89.1

(Cp), 51.2 (CH₂), 31.5 (CH₂), 25.6 (CH₂), 21.8 (CH₂), 13.4 (CH₃).

³¹P{¹H} NMR (δ, CD₂Cl₂, 20 °C): 140.8 (d, J_PP) 46.0 Hz), 80.7

(d, J_PP) 45.9 Hz).

1

C, 61.69; H, 5.22; N, 2.77. H NMR (δ, CD₂Cl₂, 20 °C): 7.91-

6.99 (m, 30H, Ph), 5.08 (1H, -CHdCPh₂), 4.16 (5H, Cp), 4.02-

3.78 (m, 1H, Prⁿ), 3.52-3.28 (m, 1H, Prⁿ), 2.69-2.42 (m, 1H,

Prⁿ), 2.40-2.20 (m, 1H, Prⁿ), 1.97-1.76 (m, 1H, NHPrⁿ), 1.51-

1.24 (m, 2H, Prⁿ), 1.22-1.00 (m, 2H, Prⁿ), 0.71 (t, J_HH) 7.1

Hz, 3H, Prⁿ), 0.59 (t, J_HH) 7.3 Hz, 3H, Prⁿ). ¹³C{¹H} NMR (δ,

CD₂Cl₂, 20 °C): 275.2 (dd, J_1,CP) 31.1 Hz, J_2,CP) 15.0 Hz,

dC), 148.0 (-CHdCPh₂), 138.2-125.4 (Ph), 92.7 (-CHdCPh₂),

85.0 (Cp), 54.7 (d, J_CP) 2.3 Hz, CH₂), 45.9 (d, J_CP) 10.0 Hz,

CH₂), 24.3 (d, J_CP) 6.9 Hz, CH₂), 22.8 (CH₂), 11.0 (CH₃), 10.8

(CH₃). ³¹P{¹H} NMR (δ, CD₂Cl₂, 20 °C): 88.6 (d, J_PP) 36.0

Hz), 75.1 (d, J_PP) 36.0 Hz).

Attempts to Crystallize 7a. Formation of [RuCp(dC-

(CH₂Buⁿ)NHPPh₂)(K²(P,P)-PPh₂OPPh₂)]CF₃SO₃(9). Crys-

tals of 9 were obtained by diffusion of Et₂O into a CH₂Cl₂

solution of 7a. ¹H NMR (δ, CD₂Cl₂, 20 °C): 7.93-7.70 (m, 4H),

7.69-7.37 (m, 16H), 7.28-7.01 (m, 4H), 5.79 (d, J_HH) 7.4 Hz,

2H), 5.2 (5H, Cp), 2.71-2.56 (m, 2H, CH₂), 1.35-0.65 (m, 9H,

Buⁿ). ¹³C{¹H} NMR (δ, CD₂Cl₂, 20 °C): 254.1 (dC), 142.5-

124.6 (Ph), 88.8 (Cp), 51.6 (CH₂), 31.5 (CH₂), 25.9 (CH₂), 21.8

(CH₂), 13.3 (CH₃). ³¹P{¹H} NMR (δ, CD₂Cl₂, 20 °C): 137.7.

[RuCp(dC(CH₂Ph)NHPh)(PPh₂NHPh)(K¹(P)-PPh₂O)]

(10a). A solution of 7a (100 mg, 0.10 mmol) in CH₂Cl₂was

passed through a column charged with neutral Al₂O₃. The

yellow product was eluted with acetonitrile, evaporated to

dryness and dried under vacuum. Yield: 47 mg (56%). Anal.

Calcd for C₄₉H₄₄N₂OP₂Ru (mol wt 839.9): C, 70.07; H, 5.28;

[RuTp(PPh₂NHPh)₂(dCdCH(Buⁿ))]SbF₆(13). A solution

of 2a (150 mg, 0.16 mmol) in CH₂Cl₂(5 mL) and 1-hexyne (55

µL, 0.48 mmol) was treated with AgSbF₆(65.2 mg, 0.19 mmol)

and stirred at room temperature for 24 h. The solution was

evaporated to dryness and the residue dissolved in CH₂Cl₂.

Insoluble materials were filtered off. On addition of Et₂O and

petroleum ether a dark yellow solid was formed, which was

washed with Et₂O and petroleum ether and dried under

vacuum. Yield: 118 mg (62%). Anal. Calcd for C₅₁H₅₂BF₆N₈P₂-

RuSb (mol wt 1185.6): C, 51.62; H, 4.42; N, 9.44. Found: C,

51.59; H, 4.47; N, 9.47. ¹H NMR (δ, CD₂Cl₂, 20 °C): 8.04-

6.47 (m, 33H, Ph, Tp), 6.27-6.13 (m, 4H, Tp), 5.89-5.78 (m,

1

N, 3.34. Found: C, 69.89; H, 5.07; N, 3.37. H NMR (δ, CD₂-

Cl₂, 20 °C): 7.90-6.62 (m, 37H, Ph, NHPh), 4.46 (5H, Cp),

3.82 (d, J_HH) 15.0 Hz, 1H, CH₂Ph), 3.56 (d, J_HH) 15.1 Hz,

1H, CH₂Ph). ¹³C{¹H} NMR (δ, CD₂Cl₂, 20 °C): 251.4 (dd, J_I,CP

) 17.6 Hz, J_2,CP) 14.6 Hz, dC), 149.7 (d, ¹J_PC) 48.3 Hz, Ph¹),

148.3 (d, ¹J_PC) 42.9 Hz, Ph¹), 144.0 (d, J_CP) 12.3 Hz, NPh¹),

1

140.3 (d, J_PC) 42.9 Hz, Ph¹), 138.8 (d, J_PC) 40.0 Hz, Ph¹),

138.3 (NPh¹), 137.6 (CH₂Ph¹), 133.8-118.0 (Ph), 87.7 (Cp), 55.3

(CH₂). ³¹P{¹H} NMR (δ, CD₂Cl₂, 20 °C): 110.6 (d, J_PP) 48.4

Hz), 79.1 (d, J_PP) 48.4 Hz).

2

2H, Tp), 5.29 (pt, J_HP) 7.3 Hz, 2H, NHPh), 4.31-4.20 (m,

1H, dCdCHBuⁿ), 2.22-2.08 (m, 2H, Buⁿ), 1.36-1.22 (m, 2H,

Buⁿ), 1.20-1.01 (m, 2H, Buⁿ), 0.66 (t, J_HH) 7.1 Hz, 3H, Buⁿ).

¹³C{¹H} NMR (δ, CD₂Cl₂, 20 °C): 369.8 (t, J_CP) 17.6 Hz, d

CdCHBuⁿ), 144.9 (Tp), 144.4 (Tp), 140.4 (t, J_CP) 4.6 Hz,

NPh¹), 137.8 (Tp), 136.4 (Tp), 132.9 (Tp), 132.3-128.6 (Ph),

121.9 (NPh⁴), 118.6 (NPh^2,6), 107.0 (dCdCHBuⁿ), 106.4 (Tp),

105.9 (Tp), 33.1 (CH₂), 21.8 (CH₂), 18.5 (CH₂), 13.8 (CH₃). ³¹P-

{¹H} NMR (δ, CD₂Cl₂, 20 °C): 67.2.

[RuCp(dC(CH₂C₆H₄Me)NHPh)(PPh₂NHPh)(K¹(P)-

PPh₂O)] (10b). A solution of 5b (80 mg, 0.08 mmol) in CH₂-

Cl₂was passed through a column charged with neutral Al₂O₃.

The yellow product was eluted with acetonitrile, evaporated

to dryness, and dried in vacuo. Yield: 56 mg (82%). Anal. Calcd

for C₅₀H₄₆N₂OP₂Ru (mol wt 853.9): C, 70.33; H, 5.43; N, 3.28.

Found: C, 70.39; H, 5.36; N, 3.36. ¹H NMR (δ, CD₂Cl₂, 20 °C):

[RuTp(K²(C,P)dC(CH₂Ph)N(Ph)PPh₂)(K¹(P)-PPh₂NHPh)]-

SbF₆(14a). A solution of complex 2a (100 mg, 0.11 mmol) in

CH₂Cl₂(5 mL) and phenylacetylene (36 µL, 0.33 mmol) was

treated with AgSbF₆(41.2 mg, 0.12 mmol) and stirred at room

temperature for 24 h. The solution was evaporated to dryness

and the residue dissolved in CH₂Cl₂. Insoluble materials were

filtered off. On addition of Et₂O and petroleum ether a dark

yellow solid was formed, which was washed with Et₂O and

petroleum ether and dried under vacuum. Yield: 108 mg

(81%). Anal. Calcd for C₅₃H₄₈BF₆N₈P₂RuSb (mol wt 1206.6):

C, 52.76; H, 4.01; N, 9.29. Found: C, 52.84; H, 4.00; N, 9.16.

¹H NMR (δ, CD₂Cl₂, 20 °C): 8.13-6.39 (m, 37H, Ph, Tp), 6.15-

7.88-6.56 (m, 36H, Ph, NHPh), 4.46 (5H, Cp), 3.76 (d, J_HH

)

14.9 Hz, 1H, CH₂Ph), 3.48 (d, J_HH) 15.0 Hz, 1H, CH₂Ph), 2.35

(3H, CH₃). ¹³C{¹H} NMR (δ, CD₂Cl₂, 20 °C): 251.5 (dd, J_1,CP

) 17.6 Hz, J_2,CP) 14.6 Hz, dC), 149.8 (d, ¹J_PC) 47.5 Hz, Ph¹),

148.3 (d, ¹J_PC) 42.9 Hz, Ph^1′), 144.0 (d, J_CP) 12.3 Hz, NPh¹),

140.2 (d, ¹J_PC) 42.9 Hz, Ph¹), 138.8 (d, ¹J_PC) 42.2 Hz, Ph^1′),

137.6 (NPh^1′), 135.5 (CH₂C₆H₄CH₃, Ph), 135.1 (CH₂C₆H₄CH₃,

Ph), 131.6-118.0 (Ph), 87.6 (Cp), 53.8 (CH₂), 20.8 (CH₃). ³¹P-

{¹H} NMR (δ, CD₂Cl₂, 20 °C): 111.1 (d, J_PP) 47.1 Hz), 79.1

(d, J_PP) 47.1 Hz).

[CpRu(PPh₂NHPh)₂(dCdCdCPh₂)]CF₃SO₃(11). A solu-

tion of complex 1 (150 mg, 0.20 mmol) in CH₂Cl₂(5 mL) and

1,1-diphenylpropyn-1-ol (124 mg, 0.6 mmol) was treated with

AgO₃SCF₃(56 mg, 0.22 mmol) and stirred at room temperature

for 8 h. The solution was evaporated to dryness and the residue

dissolved in CH₂Cl₂. Insoluble materials were filtered off. On

addition of Et₂O a dark red solid was formed, which was

washed with Et₂O and dried under vacuum. Yield: 173 mg

(82%). Anal. Calcd for C₅₇H₄₇F₃N₂P₂O₃RuS (mol wt 1060.1):

5.93 (m, 4H, Ph, Tp), 5.41-5.37 (m, 1H, Tp), 5.27-5.16 (m,

2

2H, Tp), 5.03 (d, J_HH) 11.5 Hz, 1H, CH₂Ph), 4.27 (d, J_HP

)

16.1 Hz, 1H, NHPh), 4.09 (dd, J_HH) 11.8 Hz, J_HP) 3.5 Hz,

1H, CH₂Ph). ¹³C{¹H} NMR (δ, CD₂Cl₂, 20 °C): 286.4 (dd, J_CP

) 20.7 Hz, J_CP) 12.3 Hz, dC), 145.4 (Tp), 145.2 (Tp), 143.6

(Tp), 141.6 (d, J_CP) 10.7 Hz, NPh¹), 140.0 (d, J_CP) 4.6 Hz,

NPh^1′), 137.6 (Tp), 135.9 (Tp), 135.7 (Tp), 133.2-126.7 (Ph),

Four-Membered Azaphosphacarbenes

Organometallics, Vol. 24, No. 14, 2005 3573

120.9 (NPh⁴), 117.5 (d, J_PC) 4.6 Hz, NPh^2,6), 107.0 (Tp), 106.4

(Tp), 104.7 (Tp), 48.5 (d, J_CP) 10.0 Hz, CH₂). ³¹P{¹H} NMR

(δ, CD₂Cl₂, 20 °C): 84.2 (d, J_PP) 39.7 Hz), 82.2 (d, J_PP) 39.7

Hz).

[RuTp(K²(C,P)dC(CH₂Buⁿ)N(Prⁿ)PPh₂)(K¹(P)-

PPh₂NHPrⁿ)]CF₃SO₃(15c). This complex has been prepared

analogously to 15a using 2b (100 mg, 0.12 mmol), 1-hexyne

(0.24 mmol, 27.3 µL), and AgO₃SCF₃(34 mg, 0.13 mmol) as

starting materials. Yield: 103 mg (83%). Anal. Calcd for

C₄₆H₅₆BF₃N₈O₃P₂RuS (mol wt 1031.88): C, 53.54; H, 5.47; N,

[RuTp(K²(C,P)dC(CH₂C₆H₄Me)N(Ph)PPh₂)(K¹(P)-

PPh₂NHPh)]CF₃SO₃(14b). This complex has been prepared

analogously to 14a using 2a (150 mg, 0.16 mmol), p-toluene-

acetylene (63.2 µL, 0.48 mmol), and AgO₃SCF₃(56 mg, 0.22

mmol) as starting materials. The solution was stirred at 50

°C for 48 h. Yield: 102 mg (56%). Anal. Calcd for C₅₅H₅₀-

BF₃N₈O₃P₂RuS (mol wt 1133.9): C, 58.26; H, 4.44; N, 9.88.

Found: C, 58.09; H, 4.49; N, 9.92. ¹H NMR (δ, CD₂Cl₂, 20 °C):

8.23-6.25 (m, 36H, Ph, Tp), 6.13-5.97 (m, 4H, Ph, Tp), 5.44-

5.37 (m, 1H, Tp), 5.17-5.07 (m, 2H, Tp), 4.96 (d, J_HH) 11.5

1

10.86. Found: C, 53.49; H, 5.49; N, 10.90. H NMR (δ, CD₂-

Cl₂, 20 °C): 8.05-6.22 (m, 29H, Ph, Tp), 5.99-5.76 (m, 2H,

Tp), 4.07-3.62 (m, 2H, CH₂), 3.15-2.94 (m, 1H), 2.89-2.68

(m, 1H), 2.23-1.90 (m, 2H), 1.81-1.53 (m, 3H), 1.01-0.79 (m,

10H), 0.61-0.48 (m, 6H). The NH proton could not be detected.

¹³C{¹H} NMR (δ, CD₂Cl₂, 20 °C): 286.2 (dd, J_1,CP) 22.2 Hz,

J_2,CP) 10.7 Hz, dC), 146.1 (Tp), 144.5 (d, J_CP) 3.8 Hz, Tp),

142.6 (Tp), 136.9 (Tp), 136.3 (d, J_CP) 2.3 Hz, Tp), 135.7 (Tp),

135.6-127.6 (Ph), 106.2 (Tp), 105.8 (d, J_CP) 2.3 Hz, Tp), 104.1

(Tp), 53.5 (d, J_CP) 3.1 Hz, CH₂), 46.4 (d, J_CP) 10.0 Hz, CH₂),

43.6 (d, J_CP) 10.7 Hz, CH₂), 31.9 (CH₂), 25.0 (CH₂), 24.5 (d,

J_CP) 6.1 Hz, CH₂), 24.2 (CH₂), 21.7 (CH₂), 13.1 (CH₃), 11.0

(CH₃), 10.9 (CH₃). ³¹P{¹H} NMR (δ, CD₂Cl₂, 20 °C): 87.7 (d,

J_PP) 38.5 Hz), 78.1 (d, J_PP) 38.5 Hz).

2

Hz, 1H, CH₂C₆H₄CH₃), 4.27 (d, J_HP) 15.9 Hz, 1H, NHPh),

4.07 (dd, J_1,HH) 11.3 Hz, J_2,HP) 3.7 Hz, 1H, CH₂Ph), 1.99

(3H, CH₃). ¹³C{¹H} NMR (δ, CD₂Cl₂, 20 °C): 286.5 (dd, J_1,CP

) 20.7 Hz, J_2,CP) 11.5 Hz, dC), 145.5 (Tp), 145.3 (Tp), 143.8

(Tp), 141.7 (d, J_CP) 10.7 Hz, NPh¹), 140.0 (d, J_CP) 4.6 Hz,

NPh^1′), 137.6 (Tp), 135.9 (Tp), 135.7 (Tp), 133.3-125.4 (Ph),

120.9 (NPh⁴), 117.6 (NPh^2,6), 107.0 (Tp), 106.4 (Tp), 104.5 (Tp),

48.2 (d, J_CP) 10.0 Hz, CH₂), 20.5 (CH₃). ³¹P{¹H} NMR (δ, CD₂-

Cl₂, 20 °C): 83.9 (d, J_PP) 39.7 Hz), 82.4 (d, J_PP) 39.7 Hz).

[RuTp(PPh₂NHPh)₂(dCdCdCPh₂)]CF₃SO₃(16a). A so-

lution of complex 2a (150 mg, 0.17 mmol) and 1,1-diphenyl-

propyn-1-ol (104 mg, 0.5 mmol) in CH₂Cl₂(5 mL) was treated

with AgO₃SCF₃(47 mg, 0.18 mmol) and stirred at room

temperature for 8 h. The solution was evaporated to dryness

and the residue dissolved in CH₂Cl₂. Insoluble materials were

filtered off. On addition of Et₂O and petroleum ether a dark

purple solid was obtained, which was washed with Et₂O and

petroleum ether and dried under vacuum. Yield: 138 mg

(69%). Anal. Calcd for C₆₁H₅₂BF₃N₈P₂O₃RuS (mol wt 1208.0):

C, 60.65; H, 4.34; N, 8.28. Found: C, 60.77; H, 4.41; N, 8.15.

[RuTp(K²(C,P)dC(CH₂Ph)N(Prⁿ)PPh₂)(K¹(P)-

PPh₂NHPrⁿ)]CF₃SO₃(15a). A solution of complex 2b (100

mg, 0.12 mmol) in CH₂Cl₂(5 mL) and phenylacetylene (39 µL,

0.36 mmol) was treated with AgSbF₆(34 mg, 0.13 mmol) and

stirred at room temperature for 4 h. The solution was

evaporated to dryness and the residue dissolved in CH₂Cl₂.

Insoluble materials were filtered off. On addition of Et₂O and

petroleum ether a yellow solid was formed, which was washed

with Et₂O and petroleum ether and dried under vacuum.

Yield: 103 mg (82%). Anal. Calcd. for C₄₈H₅₂BF₃N₈O₃P₂RuS

(mol wt 1051.87): C, 54.81; H, 4.98; N, 10.65. Found: C, 54.84;

¹H NMR (δ, CD₂Cl₂, 20 °C): 8.10-6.72 (m, 41H, Ph, Tp), 6.29-

2

6.14 (m, 6H, Ph, Tp), 5.72-5.64 (m, 2H, Tp), 5.51 (pt, J_HP

)

7.9 Hz, 2H, NHPh). ¹³C{¹H} NMR (δ, CD₂Cl₂, 20 °C): 312.9

(t, J_CP) 19.1 Hz, dCdCdCPh₂), 199.6 (dCdCdCPh₂), 164.1

(dCdCdCPh₂), 145 4 (Tp), 144.0 (Tp), 143.4 (Ph¹), 140.9 (t,

J_CP) 5.0 Hz, NPh¹), 137.6 (Tp), 136.0 (Tp), 133.1 (Tp), 132.3-

127.8 (Ph), 121.5 (NPh⁴), 118.2 (NPh^2,6), 106.5 (Tp), 105.4 (Tp).

³¹P{¹H} NMR (δ, CD₂Cl₂, 20 °C): 71.5.

1

H, 5.09; N, 10.58. H NMR (δ, CD₂Cl₂, 20 °C): 8.21-6.15 (m,

33H, Ph, Tp), 6.00-5.84 (m, 1H, Tp), 5.76-5.61 (m, 1H, Tp),

4.98 (d, J_HH) 13.6 Hz, 1H, CH₂Ph), 4.12-3.56 (m, 2H, Prⁿ),

3.82 (d, J_HH) 13.6 Hz, 1H, CH₂Ph), 2.26-1.87 (m, 2H, Prⁿ),

1.46-1.10 (m, 4H, Prⁿ), 0.90 (t, J_HH) 7.6 Hz, 3H, Prⁿ), 0.56

(t, J_HH) 7.6 Hz, 3H, Prⁿ). The NH proton could not be detected.

¹³C{¹H} NMR (δ, CD₂Cl₂, 20 °C): 283.7 (dd, J_1,CP) 23.0 Hz,

J_2,CP) 11.5 Hz, dC), 146.1 (Tp), 144.9 (d, J_CP) 3.1 Hz, Tp),

142.7 (Tp), 136.9 (Tp), 136.5 (Tp), 136.0 (Tp), 135.9-127.0 (Ph),

106.3 (Tp), 106.2 (Tp), 104.5 (Tp), 54.8 (d, J_CP) 2.3 Hz, CH₂),

48.9 (d, J_CP) 10.7 Hz, CH₂), 46.4 (d, J_CP) 10.0 Hz, CH₂),

24.6 (d, J_CP) 5.4 Hz, CH₂), 22.7 (CH₂), 11.0 (CH₃), 10.3 (CH₃).

³¹P{¹H} NMR (δ, CD₂Cl₂, 20°C): 86.7 (d, J_PP) 38.5 Hz), 78.6

(d, J_PP) 38.5 Hz).

[RuTp(PPh₂NHPrⁿ)₂(dCdCdCPh₂)]CF₃SO₃(16b). A so-

lution of complex 2b (100 mg, 0.12 mmol) and 1,1-diphenyl-

propyn-1-ol (50 mg, 0.24 mmol) in CH₂Cl₂(5 mL) was treated

with AgO₃SCF₃(34 mg, 0.13 mmol) and stirred at room

temperature for 1 h. The solution was evaporated to dryness

and the residue dissolved in CH₂Cl₂. Insoluble materials

were filtered off. On addition of Et₂O and petroleum ether

a dark purple solid was obtained, which was washed with

Et₂O and petroleum ether and dried under vacuum. Yield: 114

mg (83%). Anal. Calcd for C₅₅H₅₆BF₃N₈P₂O₃RuS (mol wt

1139.98): C, 57.95; H, 4.95; N, 9.83. Found: C, 58.08; H, 4.99;

[RuTp(K²(C,P)dC(CH₂C₆H₄Me)N(Prⁿ)PPh₂)(K¹(P)-

PPh₂NHPrⁿ)]CF₃SO₃(15b). This complex has been prepared

analogously to 15a using 2b (100 mg, 0.12 mmol), p-toluene-

acetylene (30.2 µL, 0.24 mmol), and AgO₃SCF₃(34 mg, 0.13

mmol) as starting materials. Yield: 116 mg (91%). Anal. Calcd

for C₄₉H₅₄BF₃N₈O₃P₂RuS (mol wt 1065.90): C, 55.22; H, 5.11;

N, 10.51. Found: C, 55.19; H, 5.19; N, 10.63. ¹H NMR (δ, CD₂-

Cl₂, 20 °C): 8.08-6.06 (m, 32H, Ph, Tp), 5.94-5.84 (m, 1H,

Tp), 5.78-5.67 (m, 1H, Tp), 4.90 (d, J_HH) 13.9 Hz, 1H, CH₂-

1

N, 9.91. H NMR (δ, CD₂Cl₂, 20 °C): 8.13-6.93 (m, 33H, Ph,

Tp), 6.65-6.46 (m, 4H, Ph, Tp), 6.43-6.32 (m, 2H, Tp), 5.77-

5.68 (m, 1H, Tp), 2.85-2.25 (m, 4H, Prⁿ), 1.71-1.44 (m, 4H,

Prⁿ), 0.91 (t, J_HH) 7.3 Hz, 6H, Prⁿ). The NH proton could not

be detected. ¹³C{¹H} NMR (δ, CD₂Cl₂, 20 °C): 316.9 (t, J_CP

)

19.9 Hz, dCdCdCPh₂), 206.1 (dCdCdCPh₂), 160.9 (dCdCd

CPh₂), 146.9-127.6 (Tp, Ph), 106.6 (Tp), 106.1 (Tp), 105.3 (Tp),

46.8 (t, J_CP) 4.6 Hz, CH₂), 25.9 (t, J_CP) 3.5 Hz, CH₂), 11.5

(CH₃). ³¹P{¹H} NMR (δ, CD₂Cl₂, 20 °C): 78.8.

Ph), 4.08-3.57 (m, 2H, Prⁿ), 3.79 (dd, J_1,HH) 14.1 Hz, J_2,HP

2.1 Hz, 1H, CH₂Ph), 2.54-1.87 (m, 2H, Prⁿ), 2.11 (3H, CH₃),

1.50-1.21 (m, 2H, Prⁿ), 1.08-0.87 (m, 2H, Prⁿ), 0.67 (t, J_HH

)

[RuTp(K²(C,P)dC(CHdCPh₂)N(Prⁿ)PPh₂)(K¹(P)-

PPh₂NHPrⁿ)]CF₃SO₃(17). A solution of complex 16b (100

mg, 0.09 mmol) in CH₂Cl₂(5 mL) was heated at 50 °C for 8 h.

The solution was reduced to about 1 mL. On addition of Et₂O

and petroleum ether a red solid was obtained which was

washed with Et₂O and petroleum ether and dried under

vacuum. Yield: 83 mg (81%). Anal. Calcd. for C₅₅H₅₆BF₃N₈P₂O₃-

RuS (mol wt 1139.98): C, 60.65; H, 4.34; N, 8.28. Found: C,

60.59; H, 4.38; N, 8.16. ¹H NMR (δ, CD₂Cl₂, 20 °C): 8.15-

6.69 (m, 33H, Ph, Tp), 6.64-6.47 (m, 2H, Ph, Tp), 6.44-6.23

(m, 4H, Ph, Tp), 5.88-5.81 (m, 1H, Tp), 5.07 (d, J_HP) 7.3 Hz,

1H, CH), 3.70-3.46 (m, 1H), 3.25-2.97 (m, 1H), 2.63-2.28 (m,

)

6.5 Hz, 3H, Prⁿ), 0.55 (t, J_HH) 7.3 Hz, 3H, Prⁿ). The NH proton

could not be detected. ¹³C{¹H} NMR (δ, CD₂Cl₂, 20 °C): 284.0

(dd, J_CP) 22.6 Hz, J_CP) 11.1 Hz, dC), 146.1 (Tp), 145.0 (d,

J_CP) 3.1 Hz, Tp), 142.8 (Tp), 137.0 (Tp), 136.4 (d, J_CP) 51.4

Hz), 136.4 (Tp), 135.9 (Tp), 135.3-127.6 (Ph), 106.3 (Tp), 106.1

(d, J_CP) 3.1 Hz, Tp), 104.5 (Tp), 54.7 (d, J_CP) 3.1 Hz, CH₂),

48.6 (d, J_CP) 10.7 Hz, CH₂), 46.4 (d, J_CP) 10.0 Hz, CH₂),

24.5 (d, J_CP) 6.1 Hz, CH₂), 22.7 (CH₂), 20.5 (CH₃), 11.0 (CH₃),

10.3 (CH₃). ³¹P{¹H} NMR (δ, CD₂Cl₂, 20 °C): 87.0 (d, J_PP

38.5 Hz), 78.4 (d, J_PP) 38.5 Hz).

)

3574 Organometallics, Vol. 24, No. 14, 2005

Pavlik et al.

Table 1. Details for the Crystal Structure Determinations of Complexes 1a, 2a‚CHCl₃, 3, 4‚solv, and 9

1a

2a‚CHCl₃

3

4‚solv

9

formula

C

₄₁H₃₇ClN₂P₂Ru

C₄₆H₄₃BCl₄N₈P₂Ru

1023.50

0.60 × 0.36 × 0.20

P2₁/n (14)

11.005(2)

21.850(3)

20.272(3)

90

C₄₂H₃₇F₃N₂O₃P₂RuS

869.81

0.6 × 0.4 × 0.3

Pn (7)

9.9429(12)

21.374(3)

18.606(2)

90

C₄₁H₃₇F₆N₂P₂RuSb

956.49

C₄₂H₄₂F₃NO₄P₂RuS

876.84

fw

756.19

0.62 × 0.54 × 0.40

P2₁(4)

10.0363(6)

18.0314(11)

10.3864(6)

90

cryst size, mm

0.70 × 0.25 × 0.20

P2₁/n (14)

11.142(2)

15.037(3)

24.940(4)

90

0.75 × 0.42 × 0.22

space group (No.)

P1h (2)

a, Å

11.6571(7)

12.9967(8)

15.1889(9)

77.718(1)

68.636(1)

71.892(1)

2024.0(2)

2

b, Å

c, Å

R, deg

â, deg

γ, deg

V, Å³

Z

113.968(1)

90

1717.5(2)

2

1.462

100(2)

0.660

776

30

32 068

9955

9932

430

0.0167

0.0168

0.0443

-0.26/0.40

103.544(2)

90

98.610(2)

90

100.654(3)

90

4738.7(12)

4

3909.6(8)

4

4106.5(12)

4

F

_calcd, g cm^-3

1.435

1.478

1.547

1.439

T, K

123(2)

297(2)

173(2)

300(2)

µ(Mo KR), mm^-1

F(000)

θ_max, deg

0.666

0.592

1.161

0.574

2088

1776

1904

900

30

25

30

no. of rflns measd

no. of unique rflns

no. of rflns I > 2σ(I)

no. of params

R1 (I > 2σ(I))^a

R1 (all data)

67 859

29 072

19 397

15 960

987

27 305

28 295

13 633

6922

11 591

11 898

5232

9669

598

508

629

0.0291

0.0315

0.0450

0.0745

-0.42/0.35

0.0468

0.0344

0.0360

0.0735

0.0444

wR2 (all data)^a

diff Fourier peaks

min/max, e Å^-3

0.0738

0.1076

0.0912

-0.50/0.76

-0.70/1.47

-0.74/0.77

2

^aR1 ) ∑||F_o| - |F_c||/∑|F_o|; wR2 ) [∑(w(F_o- F_c)²)/∑(w(F_o²)²)]^1/2

.

Table 2. Details for the Crystal Structure Determinations of Complexes 10a, 11‚CH₂Cl₂, 14a‚2C₆H₅F,

15b‚CH₂Cl₂, and 17

10a

11‚CH₂Cl₂

14a‚2C₆H₅F

15b‚CH₂Cl₂

17

formula

C

₄₉H₄₄N₂OP₂Ru

C₅₈H₄₉Cl₂F₃N₂O₃-

P₂RuS

C

₆₅H₅₈BF₈N₈P₂RuSb

C₅₀H₅₆BCl₂F₃N₈O₃-

P₂RuS

1150.81

0.70 × 0.50 × 0.32

P1h (2)

C

₅₅H₅₆BF₃N₈O₃-

P₂RuS

fw

839.87

0.2 × 0.1 × 0.1

P2₁/c (14)

19.82(4)

8.626(15)

23.59(4)

90

100.61(5)

90

3964(13)

4

1.407

1144.96

0.53 × 0.36 × 0.22

P2₁/n (14)

13.280(2)

12.787(2)

31.996(5)

90

1398.76

0.12 × 0.04 × 0.02

P2₁/c (14)

11.403(2)

17.341(4)

31.492(7)

90

96.726(7)

90

6184(2)

4

1.502

300(2)

0.805

2824

23.1

28 346

8639

3246

555

1139.96

0.68 × 0.33 × 0.19

P1h (2)

cryst size, mm

space group (No.)

a, Å

12.8141(5)

13.9087(6)

18.1289(7)

86.685(1)

69.964(1)

62.774(1)

2680.2(2)

2

12.3228(5)

13.8390(5)

17.7616(7)

79.910(1)

83.886(1)

63.820(1)

2674.7(2)

2

b, Å

c, Å

R, deg

â, deg

γ, deg

V, Å³

Z

100.455(3)

90

5343.1(14)

4

F

_calcd, g cm^-3

1.423

1.426

1.415

T, K

300(2)

0.517

173(2)

µ(Mo KR), mm^-1

F(000)

θ_max, deg

0.549

0.550

0.454

1736

2344

1184

1176

25

30

no. of rflns measd

no. of unique rflns

no. of rflns I > 2σ(I)

no. of params

R1 (I > 2σ(I)) ^a

R1 (all data)

9230

30 407

50 111

50 109

6115

9336

15 449

15 487

2442

5480

14 225

14 512

410

583

676

717

0.0905

0.2121

0.2007

-0.62/0.85

0.0641

0.0874

0.2321

0.2634

-0.53/0.77

0.0272

0.0249

0.1245

0.0303

0.0268

wR2 (all data)^a

diff Fourier peaks

min/max, e Å^-3

0.1834

0.0743

0.0667

-0.78/1.11

-0.66/0.53

-0.32/0.46

2

^aR1 ) ∑||F_o| - |F_c||/∑|F_o|; wR2 ) [∑(w(F_o- F_c)²)/∑(w(F_o²)²)]^1/2

.

2H), 2.27-2.09 (m, 1H), 2.03-1.84 (m, 1H), 1.67-1.39 (m, 2H),

0.88-0.75 (m, 3H), 0.64-0.44 (m, 3H). The NH proton could

not be detected. ¹³C{¹H} NMR (δ, CD₂Cl₂, 20 °C): 274.8 (dd,

J_CP) 22.2 Hz, J_CP) 13.0 Hz, dC), 152.5 (-CHdCPh₂), 146.3-

129.9 (Tp, Ph), 129.7 (-CHdCPh₂), 129.6-127.0 (Ph), 106.7

(Tp), 106.0 (Tp), 105.1 (Tp), 56.9 (d, J_CP) 2.3 Hz, CH₂), 46.0

(d, J_CP) 10.0 Hz, CH₂), 24.5 (d, J_CP) 6.1 Hz, CH₂), 22.2 (CH₂),

11.0 (CH₃), 10.9 (CH₃). ³¹P{¹H} NMR (δ, CD₂Cl₂, 20 °C): 83.4

(d, J_PP) 39.7 Hz), 80.2 (d, J_PP) 39.7 Hz).

X-ray Structure Determination. Crystals of 1a, 2a‚

CHCl₃, 3, 4‚solv, 9, 10a, 11‚CH₂Cl₂, 14a‚2C₆H₅F, 15b‚CH₂Cl₂,

and 17 were obtained by diffusion of Et₂O or pentane (4‚solv,

15b‚CH₂Cl₂, 17) into CH₂Cl₂or CHCl₃(2a‚CHCl₃) solutions.

Compound 9 cocrystallized with 10a from CH₂Cl₂/Et₂O. In the

case of complex 14a this method gave only very unstable

solvates, which were not measurable at all. Finally, evapora-

tion crystallization from fluorobenzene was successful and

yielded well-developed stable crystals of a corresponding

solvate with the disadvantage of a very small size. Crystal data

and experimental details are given in Tables 1 and 2. X-ray

data were collected on a Bruker Smart APEX CCD area

detector diffractometer using graphite-monochromated Mo KR

radiation (λ ) 0.710 73 Å) and 0.3° ω-scan frames covering

either hemispheres or complete spheres of the reciprocal space,

except for 9, where a quarter-sphere was measured. Correc-

tions for absorption (multiscan method), λ/2 effects, and crystal

Four-Membered Azaphosphacarbenes

Organometallics, Vol. 24, No. 14, 2005 3575

decay were applied.³³The structures were solved by direct

methods using the program SHELXS97.³⁴Structure refine-

ment on F²was carried out with the program SHELXL97.³³

All non-hydrogen atoms were refined anisotropically. Hydro-

gen 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 permitted by data quality.³⁵

Computational Details. All calculations were performed

using the Gaussian98 software package.³⁶The geometries of

the model complexes and the transition states were optimized

at the B3LYP level³⁷with the Stuttgart/Dresden ECP (SDD)

basis set.³⁸For all other atoms the 6-31G(d,p) basis set was

employed.³⁹A vibrational analysis was performed to confirm

that the structures of the model compounds have no imaginary

frequency. The geometries were optimized without symmetry

constraints.

Acknowledgment. Financial support by the “Fonds

zur Fo¨rderung der wissenschaftlichen Forschung” is

gratefully acknowledged (Project No. P16600-N11).

Supporting Information Available: Complete crystal-

lographic data and technical details in CIF format for 1a, 2a‚

CHCl₃, 3, 4‚solv, 9, 10a, 11‚CH₂Cl₂, 14a‚2C₆H₅F, 15b‚CH₂Cl₂,

and 17. This material is available free of charge via the

Internet at http://pubs.acs.org.

(33) Bruker programs: SMART, version 5.054; SAINT, version 6.2.9;

SADABS, version 2.03; XPREP, version 5.1; SHELXTL, version 5.1

(Bruker AXS Inc., Madison, WI, 2001).

(34) Sheldrick, G. M. SHELX97: Program System for Crystal

Structure Determination; University of Go¨ttingen, Go¨ttingen, Ger-

many, 1997.

OM050247A

(35) Spek, A. L. PLATON: A Multipurpose Crystallographic Tool;

University of Utrecht, Utrecht, The Netherlands, 2003.

(36) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.;

Robb, M. A.; Cheeseman, J. R.; Zakrzewski, V. G.; Montgomery, J. A.,

Jr.; Stratmann, R. E.; Burant, J. C.; Dapprich, S.; Millam, J. M.;

Daniels, A. D.; Kudin, K. N.; Strain, M. C.; Farkas, O.; Tomasi, J.;

Barone, V.; Cossi, M.; Cammi, R.; Mennucci, B.; Pomelli, C.; Adamo,

C.; Clifford, S.; Ochterski, J.; Petersson, G. A.; Ayala, P. Y.; Cui, Q.;

Morokuma, K.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.;

Foresman, J. B.; Cioslowski, J.; Ortiz, J. V.; Stefanov, B. B.; Liu, G.;

Liashenko, A.; Piskorz, P.; Komaromi, I.; Gomperts, R.; Martin, R. L.;

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Article Doi

Reactions of the cationic fragments [RuCp(PPh2NHR) 2]+ and [RuTp(PPh2NHR)2]+ (R = Ph, re-Pr) with Alkynes: Formation of four-membered azaphosphacarbenes

DOI: 10.1021/om050247a

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