TRUST PREFERRED SECURITIES GUARANTEE AGREEMENT

Exhibit 4.5

EXECUTION VERSION

TRUST PREFERRED SECURITIES GUARANTEE AGREEMENT

The PNC Financial Services Group, Inc.

(as Guarantor)

and

The Bank of New York

(as Trust Preferred Guarantee Trustee)

Dated as of February 13, 2008

TABLE OF CONTENTS

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TRUST PREFERRED SECURITIES GUARANTEE AGREEMENT

This GUARANTEE AGREEMENT (the “Trust Preferred Securities Guarantee”), dated as of February 13, 2008, is executed and delivered by The PNC Financial Services Group, Inc., a Pennsylvania corporation, and The Bank of New York, a New York corporation as trustee, for the benefit of the Holders (as defined herein) from time to time of the Trust Preferred Securities (as defined herein) of PNC Capital Trust E, a Delaware statutory trust (the “Trust”).

WHEREAS, pursuant to the Second Amended and Restated Declaration of Trust (the “Declaration”), dated as of February 13, 2008, among the trustees of the Trust named therein, the Guarantor, as sponsor, and the holders from time to time of preferred undivided beneficial interests in the assets of the Trust, the Trust is issuing on the date hereof 18,000,000 trust preferred securities, having an aggregate liquidation amount of $450,000,000, designated the 7  ³ / 4 % Trust Preferred Securities (the “Trust Preferred Securities”);

WHEREAS, as incentive for the Holders to purchase the Trust Preferred Securities, the Guarantor desires irrevocably and unconditionally to agree, to the extent set forth in this Trust Preferred Securities Guarantee, to pay to the Holders the Guarantee Payments (as defined herein) and to make certain other payments on the terms and conditions set forth herein.

NOW, THEREFORE, in consideration of the purchase by each Holder of Trust Preferred Securities, which purchase the Guarantor hereby agrees shall benefit the Guarantor, the Guarantor executes and delivers this Trust Preferred Securities Guarantee for the benefit of the Holders.

ARTICLE I

DEFINITIONS AND INTERPRETATION

SECTION 1.1 Definitions and Interpretation

In this Trust Preferred Securities Guarantee, unless the context otherwise requires:

(a) Capitalized terms used in this Trust Preferred Securities Guarantee but not defined in the preamble above have the respective meanings assigned to them in this Section 1.1;

(b) a term defined anywhere in this Trust Preferred Securities Guarantee has the same meaning throughout;

(c) all references to “the Trust Preferred Securities Guarantee” or “this Trust Preferred Securities Guarantee” are to this Trust Preferred Securities Guarantee as modified, supplemented or amended from time to time;

(d) all references in this Trust Preferred Securities Guarantee to Articles and Sections are to Articles and Sections of this Trust Preferred Securities Guarantee, unless otherwise specified;

(e) a term defined in the Trust Indenture Act has the same meaning when used in this Trust Preferred Securities Guarantee, unless otherwise defined in this Trust Preferred Securities Guarantee or unless the context otherwise requires; and

(f) a reference to the singular includes the plural and vice versa.

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“Act” by any Holder means any instrument or instruments (and the action embodied therein and evidenced thereby) embodying or evidencing any request, demand, authorization, direction, notice, consent, waiver or other action provided or permitted by the Indenture to be given or taken by Holders signed by such Holders in person or by an agent duly appointed in writing. Proof of execution of any such instrument or of a writing appointing any such agent shall be sufficient for any purpose of this Guarantee and (subject to Section 3.1) conclusive in favor of the Trust Preferred Guarantee Trustee and the Guarantor, if made in the manner provided in Section 1.04 of the Indenture.

“Affiliate” of any specified Person means any other Person directly or indirectly controlling or controlled by or under direct or indirect common control with such specified Person. For the purposes of this definition, “control” when used with respect to any specified Person means the power to direct the management and policies of such Person, directly or indirectly, whether through the ownership of voting securities, by contract or otherwise; and the terms “controlling” and “controlled” have meanings correlative to the foregoing.

“Board of Directors” means either the board of directors of the Guarantor or any committee of that board duly authorized to act hereunder.

“Board Resolution” means a copy of a resolution certified by the Secretary or an Assistant Secretary of the Guarantor to have been duly adopted by the Board of Directors and to be in full force and effect on the date of such certification, and delivered to the Trust Preferred Guarantee Trustee.

“Business Day” means any day other than a Saturday, Sunday or any other day on which banking institutions in the City of New York, New York, the City of Pittsburgh, Pennsylvania, the Commonwealth of Pennsylvania or the City of Wilmington, Delaware are authorized or obligated by any applicable law, regulation or executive order to close.

“Commission” means the Securities and Exchange Commission as from time to time constituted, created under the Securities and Exchange Act of 1934, as amended, or, if at any time after the execution of this Trust Preferred Securities Guarantee such Commission is not existing and performing the duties now assigned to it under the Trust Indenture Act, then the body performing such duties at such time.

“Corporate Trust Office” means the principal office of the Trust Preferred Guarantee Trustee at which at any particular time its corporate trust business shall be administered, which on the date hereof is located at 101 Barclay Street, Floor 8 West, New York, New York 10286.

“Covered Person” means any Holder or beneficial owner of Trust Preferred Securities.

“JSNs” means the 7  ³ / 4 % Junior Subordinated Notes due March 15, 2068 to be issued by the Trust under the Indenture held by the Property Trustee (as defined in the Declaration).

“Distribution” has the meaning set forth in the Declaration.

“Event of Default” means (i) a default by the Guarantor of any of its payment obligations under this Trust Preferred Securities Guarantee or (ii) a default by the Guarantor in any other obligation under this Trust Preferred Securities Guarantee that remains unremedied for 30 days.

“First Supplemental Indenture” means the First Supplemental Indenture, dated as of February 13, 2008, between the Guarantor and The Bank of New York, as trustee.

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“Guarantee Payments” means the following payments or distributions, without duplication, with respect to the Trust Preferred Securities, to the extent not paid or made by the Trust: (i) any accumulated and unpaid Distributions that are required to be paid on the Trust Preferred Securities, to the extent the Trust has funds available therefor, (ii) the Redemption Price, when required to be paid, with respect to any Trust Preferred Securities called for redemption by the Trust, to the extent that the Trust has funds available therefor and (iii) upon a voluntary or involuntary dissolution, winding-up or liquidation of the Trust (other than in connection with the distribution of JSNs to the Holders in exchange for Trust Preferred Securities as provided in the Declaration) the lesser of (a) the aggregate of the liquidation amount of $25 per Trust Preferred Security and all accumulated and unpaid Distributions on the Trust Preferred Securities to the date of payment, to the extent the Trust has funds available therefor or (b) the amount of assets of the Trust remaining available for distribution to Holders in liquidation of the Trust (in either case, the “Liquidation Distribution”).

“Guarantor” means The PNC Financial Services Group, Inc. until a successor Person shall have become such pursuant to the applicable provisions of this Trust Preferred Securities Guarantee, and thereafter “Guarantor” shall mean such successor Person.

“Holder” means a Person in whose name a Certificate representing a Trust Preferred Security is registered in the Security Register; provided that in determining whether the holders of the requisite percentage of Trust Preferred Securities have given any request, notice, consent or waiver hereunder, “Holder” shall not include the Guarantor, the Trust Preferred Guarantee Trustee, or any Affiliate of the Guarantor or the Trust Preferred Guarantee Trustee.

“Indemnified Person” means the Trust Preferred Guarantee Trustee, any Affiliate of the Trust Preferred Guarantee Trustee, or any officers, directors, shareholders, members, partners, employees, representatives, nominees, custodians or agents of the Trust Preferred Guarantee Trustee.

“Indenture” means the Amended and Restated Junior Subordinated Indenture, dated as of February 13, 2008 (as supplemented and amended by the First Supplemental Indenture), between the Guarantor and The Bank of New York, as trustee, pursuant to which the JSNs are to be issued.

“Liquidation Amount” means the stated amount of $25 per Trust Preferred Security.

“Liquidation Distribution” has the meaning set forth in the Definition of Guarantee Payments.

“List of Holders” has the meaning set forth in Section 2.2(a).

“Majority in Liquidation Amount of the Trust Preferred Securities” means, except as provided in the terms of the Trust Preferred Securities or by the Trust Indenture Act, Holder(s) of outstanding Trust Preferred Securities voting together as a single class who are the record holders of an aggregate Liquidation Amount representing more than 50% of the aggregate Liquidation Amount of all then outstanding Trust Preferred Securities.

“Officers’ Certificate” means a certificate signed by the Chairman or any Vice Chairman of the Board of Directors, President or a Vice President, and by its Treasurer, an Assistant Treasurer, Controller, an Assistant Controller, Secretary or an Assistant Secretary, of the Guarantor, and delivered to the Trust Preferred Guarantee Trustee.

“Person” means any individual, corporation, partnership, limited liability company, joint venture, association, joint stock company, trust, unincorporated organization or government or any agency or political subdivision thereof or any other entity.

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“Property Trustee” has the meaning set forth in the Declaration.

“Responsible Officer” means, with respect to the Trust Preferred Guarantee Trustee, any officer within the Corporate Trust Office of the Trust Preferred Guarantee Trustee with direct responsibility for the administration of this Trust Preferred Securities Guarantee and also means, with respect to a particular corporate trust matter, any other officer to whom such matter is referred because of that officer’s knowledge of and familiarity with the particular subject.

“Redemption Price” has the meaning set forth in the Indenture.

“Security Register” has the meaning set forth in the Declaration.

“Trust Indenture Act” means the Trust Indenture Act of 1939 (15 U.S.C. §§ 77aaa-77bbb), as amended and as in effect on the date as of this Indenture, except that any amendments hereto shall conform to the requirements of the Trust Indenture Act as then in effect.

“Trust Preferred Guarantee Trustee” means The Bank of New York until a successor Trust Preferred Guarantee Trustee shall have become such pursuant to the applicable provisions of this Trust Preferred Securities Guarantee, and thereafter “Trust Preferred Guarantee Trustee” shall mean or include each such Person who is then a Trust Preferred Guarantee Trustee hereunder.

“Underwriting Agreement” has the meaning set forth in the Declaration.

ARTICLE II

TRUST INDENTURE ACT

SECTION 2.1 Trust Indenture Act; Application

If any provision hereof limits, qualifies or conflicts with a provision of the Trust Indenture Act that is required or deemed under such Act to be a part of and govern this Trust Preferred Securities Guarantee, the required or deemed provision shall control. If any provision of this Trust Preferred Securities Guarantee modifies or excludes any provision of the Trust Indenture Act that may be so modified or excluded under such Act, the modified or excluded provision shall be deemed to apply to this Trust Preferred Securities Guarantee as so modified or to be excluded, as the case may be.

SECTION 2.2 Lists of Holders of Trust Preferred Securities

(a) The Guarantor shall provide the Trust Preferred Guarantee Trustee (i) within 15 days after each record date for payment of Distributions, a list, in such form as the Property Trustee may reasonably require, of the names and addresses of the Holders of the Securities (“List of Holders”) as of such record date, provided , that neither the Guarantor nor the Trust Preferred Guarantee Trustee shall be obligated to provide such List of Holders at any time if the List of Holders does not differ from the most recent List of Holders given to the Trust Preferred Guarantee Trustee by the Guarantor, and (ii) at any other time, within 30 days of receipt by the Guarantor of a written request for a List of Holders as of a date no more than 14 days before such List of Holders is given to the Trust Preferred Guarantee Trustee. The Trust Preferred Guarantee Trustee shall preserve, in as current a form as is reasonably practicable, all information contained in Lists of Holders given to it, provided, that the Trust Preferred Guarantee Trustee may destroy any List of Holders previously given to it on receipt of a new List of Holders.

(b) The Trust Preferred Guarantee Trustee shall comply with its obligations under §§ 311(a), 311(b) and 312(b) of the Trust Indenture Act.

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SECTION 2.3 Reports by the Trust Preferred Guarantee Trustee

Within 60 days after May 15 of each year commencing with the year 2008, the Trust Preferred Guarantee Trustee shall transmit to the Holders of the Trust Preferred Securities for which it is Trust Preferred Guarantee Trustee hereunder, as their names and addresses appear in the Securities Register, a brief report dated as of such May 15 in accordance with, and to the extent required under, Section 313 of the Trust Indenture Act.

SECTION 2.4 Periodic Reports to Trust Preferred Guarantee Trustee

The Guarantor shall:

(a) file with the Trust Preferred Guarantee Trustee, within 15 days after the Guarantor is required to file the same with the Commission, copies of the annual reports and of the information, documents and other reports (or copies of such portions of any of the foregoing as the Commission may from time to time by rules and regulations prescribe) which the Commission may be required to file, and such summaries thereof, as may be required pursuant to the Trust Indenture Act at the times and in the manner provided in the Trust Indenture Act; provided that any such information, documents or reports required to be filed with the Commission pursuant to Section 13 or Section 15(d) of the Exchange Act; or, if the Guarantor is not required to file information, documents or reports pursuant to either of said Sections, then it shall file with the Trust Preferred Guarantee Trustee and the Commission, in accordance with the rules and regulations prescribed from time to time by the Commission, such of the supplementary and periodic information, documents and reports which may be required pursuant to Section 13 of the Exchange Act in respect of a security listed and registered on a national securities exchange as may be prescribed from time to time in such rules and regulations;

(b) file with the Trust Preferred Guarantee Trustee and the Commission, in accordance with the rules and regulations prescribed from time to time by the Commission, such additional information, documents and reports with respect to compliance by the Guarantor with the conditions and covenants of this Trust Preferred Securities Guarantee as may be required from time to time by such rules and regulations; and

(c) transmit by mail to all Holders, as their names and addresses appear in the Securities Register, within 30 days after the filing thereof with the Trust Preferred Guarantee Trustee, such summaries of any information, documents and reports required to be filed by the Guarantor pursuant to paragraphs (a) and (b) of this Section 2.4 as may be required by rules and regulations prescribed from time to time by the Commission.

Delivery of such reports, information and documents to the Trust Preferred Guarantee Trustee is for informational purposes only and the Trust Preferred Guarantee Trustee’s receipt of such reports shall not constitute constructive notice of any information contained therein or determinable from information contained therein, including the Guarantor’s compliance with any of its covenants hereunder (as to which the Trust Preferred Guarantee Trustee is entitled to rely exclusively on Officers’ Certificates).

SECTION 2.5 Evidence of Compliance with Conditions Precedent

The Guarantor shall provide to the Trust Preferred Guarantee Trustee such evidence of compliance with any conditions precedent, if any, provided for in this Trust Preferred Securities Guarantee that relate to any of the matters set forth in Section 314(c) of the Trust Indenture Act or as required by Section 314(c). Any certificate required to be given by an officer pursuant to Section 314(c)(1) of the Trust Indenture Act may be given in the form of an Officers’ Certificate.

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SECTION 2.6 Compliance Certificate and Opinions

Upon any application or request by the Guarantor to the Trust Preferred Guarantee Trustee to take any action under any provision of this Trust Preferred Securities Guarantee, the Guarantor shall furnish to the Trust Preferred Guarantee Trustee an Officers’ Certificate stating that all conditions precedent, if any, provided for in this Trust Preferred Securities Guarantee relating to the proposed action have been complied with and an Opinion of Counsel stating that in the opinion of such counsel all such conditions precedent, if any, have been complied with.

Any Officers’ Certificate or Opinion of Counsel delivered with respect to compliance with a condition or covenant provided for in this Trust Preferred Securities Guarantee shall include:

(a) a statement that each individual signing the Officers’ Certificate or Opinion of Counsel has read such covenant or condition and the definitions herein relating thereto;

(b) a brief statement as to the nature and scope of the examination or investigation upon which the statements or opinions contained in the Officers’ Certificate or Opinion of Counsel are based;

(c) a statement that, in the opinion of each such individual, he or she has made such examination or investigation as is necessary to enable him or her to express an informed opinion as to whether or not such covenant or condition has been complied with; and

(d) a statement as to whether, in the opinion of each such individual, such condition or covenant has been complied with.

SECTION 2.7 Events of Default; Waiver

The Holders of a Majority in Liquidation Amount of Trust Preferred Securities may, by vote, on behalf of the Holders of all of the Trust Preferred Securities, waive any past Event of Default and its consequences. Upon such waiver, any such Event of Default shall cease to exist, and any Event of Default arising therefrom shall be deemed to have been cured, for every purpose of this Trust Preferred Securities Guarantee, but no such waiver shall extend to any subsequent or other default or Event of Default or impair any right consequent thereon.

SECTION 2.8 Event of Default; Notice

(a) The Trust Preferred Guarantee Trustee shall, within 60 days after the occurrence of an Event of Default, transmit by mail, first class postage prepaid, to the Holders, notices of all Events of Default actually known to a Responsible Officer of the Trust Preferred Guarantee Trustee as being an Event of Default hereunder, unless such Events of Default have been cured before the giving of such notice; provided , that the Trust Preferred Guarantee Trustee shall be protected in withholding such notice if and so long as a Responsible Officer of the Trust Preferred Guarantee Trustee in good faith determines that the withholding of such notice is in the interests of the Holders.

(b) The Trust Preferred Guarantee Trustee shall not be deemed to have knowledge of any Event of Default unless either the Trust Preferred Guarantee Trustee shall have received written notice thereof, or a Responsible Officer charged with the administration of this Trust Preferred Securities Guarantee shall have actual knowledge.

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SECTION 2.9 Conflicting Interests

The Declaration shall be deemed to be specifically described in this Trust Preferred Securities Guarantee for the purposes of clause (i) of the first proviso contained in Section 310(b) of the Trust Indenture Act.

ARTICLE III

POWERS, DUTIES AND RIGHTS OF

TRUST PREFERRED GUARANTEE TRUSTEE

SECTION 3.1 Powers and Duties of the Trust Preferred Guarantee Trustee

(a) This Trust Preferred Securities Guarantee shall be held by the Trust Preferred Guarantee Trustee for the benefit of the Holders, and the Trust Preferred Guarantee Trustee shall not transfer its right, title and interest in this Trust Preferred Securities Guarantee to any Person except a Holder exercising his or her rights pursuant to Sections 5.4(b) and 5.4(c) or to a successor Trust Preferred Guarantee Trustee on acceptance by such successor Trust Preferred Guarantee Trustee of its appointment to act as successor Trust Preferred Guarantee Trustee. The right, title and interest of the Trust Preferred Guarantee Trustee shall automatically vest in any successor Trust Preferred Guarantee Trustee, and such vesting and cessation of title shall be effective whether or not conveyancing documents have been executed and delivered pursuant to the appointment of such successor Trust Preferred Guarantee Trustee.

(b) If an Event of Default actually known to a Responsible Officer as an Event of Default has occurred and is continuing, the Trust Preferred Guarantee Trustee shall enforce this Trust Preferred Securities Guarantee for the benefit of the Holders of the Trust Preferred Securities.

(c) The Trust Preferred Guarantee Trustee, before the occurrence of any Event of Default and after the curing of all Events of Default that may have occurred, shall undertake to perform only such duties as are specifically set forth in this Trust Preferred Securities Guarantee, and no implied covenants shall be read into this Trust Preferred Securities Guarantee against the Trust Preferred Guarantee Trustee. In case an Event of Default has occurred (that has not been cured or waived pursuant to Section 2.7) and is actually known to a Responsible Officer, the Trust Preferred Guarantee Trustee shall exercise such of the rights and powers vested in it by this Trust Preferred Securities Guarantee, and use the same degree of care and skill in its exercise thereof, as a prudent person would exercise or use under the circumstances in the conduct of his or her own affairs.

(d) Except during the continuance of Event of Default:

(i) the Trust Preferred Guarantee Trustee shall undertake to perform only such duties as are specifically set forth in this Trust Preferred Securities Guarantee and no implied covenants shall be read into this Trust Preferred Securities G